TW200821292A - Compound, acid generator, resist composition, and resist pattern forming method - Google Patents

Abstract

This resist composition is a resist composition which includes (A) a resin component whose alkali solubility varies by an action of an acid, and (B) an acid generator component which generates an acid upon exposure, wherein the component (B) contains (B1) an acid generator represented by the following general formula (b1-3):[Chemical Formula 1] wherein R41, R42, and R43 each independently represents alkyl group, acetyl group, alkoxy group, carboxyl group, hydroxyl group, or hydroxyalkyl group; n1 represents a integer from 0 to 3; n2 represents a integer from 0 to 3; and n3 represents a integer from 0 to 2; n1, n2, and n3 are not 0 simultaneously; and X- represents an anion.

Description

200821292 IX. The present invention relates to a compound suitable as an acid generator for a photoresist composition, an acid generator formed of the compound, and a photoresist composition containing the acid generator. And a method of forming a photoresist pattern using the photoresist composition. This case is based on the special wish 20 06-20 1 007 proposed by the Japan Patent Office on July 24, 2006. In this specification, B is used. [Prior Art] In the lithography lithography technique, for example, a photoresist film obtained from a photoresist material is formed on a substrate, and for the above-mentioned photoresist film, radiation such as light or electron lines is formed by forming a reticle of a specific pattern. The selective exposure is carried out by applying a development treatment to form the photoresist film into a photoresist pattern having a specific shape. The exposed portion is changed to have a photoresist which is dissolved in the developing solution. The material is called a positive type, and the exposed portion is changed to have a property of not dissolving in the developing solution. In recent years, in the manufacture of semiconductor elements or liquid crystal display elements, with the advancement of the lithography technique, the pattern has been rapidly refined. The method of miniaturization is generally performed in such a manner as to shorten the wavelength of the exposure light source. Specifically, ultraviolet rays which are represented by g-line and i-line are conventionally used. However, KrF excimer lasers or ArF excimer lasers are now being used for mass production of semiconductor components. Further, F2 excimer lasers, electron beams, EUV (200821292 extreme ultraviolet rays) or X-rays having shorter wavelengths for the aforementioned quasi-molecular lasers have also been studied. The photoresist material is intended to have sensitivity to the aforementioned exposure light source, and has lithographic etching characteristics such as resolvability of a reproducible fine-size pattern. The photoresist material which satisfies the above requirements is generally used to contain a base resin which changes the alkali solubility based on the action of an acid, and an enhanced chemical type resist which generates an acid generator by exposure. For example, a positive type of enhanced chemical type photoresist, which is a resin containing an acid-based action as a base resin to increase alkali solubility, and a B acid generator component which is formed by exposure to an acid when exposed in a photoresist pattern The generating agent generates an acid to make the exposed portion alkali-soluble. Up to now, the base resin for enhancing chemical resist is a polyhydroxystyrene (PHS) which is highly transparent to KrF excimer laser (248 nm) or a resin which is protected by an acid-dissociable dissolution inhibiting group (PHS) Resin). However, since the PHS-based resin has an aromatic ring such as a benzene ring, transparency to a shorter wavelength of 248 nm, for example, light of 193 nm is still insufficient. Therefore, the use of the PHS-based resin as the base resin component # of the enhanced chemical type photoresist, for example, for the process using 193 nm light, there are still disadvantages such as low resolution. Therefore, at present, the base resin for the photoresist used in the AtF excimer laser lithography etching has a good transparency in the vicinity of 193 nm, so that the main chain has a (meth) acrylate. Derived structural unit resin (acrylic resin). In the case of a positive type, the above-mentioned resin is mainly a structural unit derived from a (meth) acrylate containing a third-stage alkyl ester type acid dissociable dissolution inhibiting group having an aliphatic polycyclic group, for example, a main use contains 2 —Alkyl-2-adamantyl (methyl)propene-6-200821292 A resin having a structural unit derived from an enoate or the like (for example, Patent Document 1). Further, "acrylic acid ester" means one or both of an acrylate having a hydrogen atom bonded to the α-position and a methyl acrylate bonded to the α-position. "(Meth)acrylate" means an acrylate having a hydrogen atom bonded to the α-position and one or both of a methyl methacrylate bonded to the α-position. "(Meth)acrylic acid" means an acrylic acid having a hydrogen atom bonded to the α-position, and one or both of the methyl group's methacrylic acid bonded to the α-position. Further, various types of substances have been proposed for enhancing acid generators used in chemical resists, such as iron salt acid generators such as iodine salt or mirror salt, and sulfonate acid generators. A variety of 'known compounds, such as a diazomethane acid generator, a nitrobenzyl sulfonate acid generator, an imidosulfonate acid generator, and a diterpenoid acid generator. At present, an acid generator containing a triphenylsulfonium skeleton, a dinaphthylmonophenylphosphonium skeleton or the like has been used as the acid generator. (Patent Document 2). [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. 2005-100203 [Patent Document 2] In recent years, high resolution has been achieved with the miniaturization of the photoresist pattern. With further expectations, there is an increase in the lithography characteristics sought. At present, the cation of the key salt acid generator generally uses a highly hydrophobic cation such as triphenylsulfonium or dinaphthylmonophenylphosphonium, but has the above-mentioned cation key salt acid generator for dissolving the photoresist. The organic solvent (photoresist solvent) used in various ingredients of 200821292 has a problem of low solubility. The low solubility of the above-mentioned photoresist solvent causes a decrease in the storage stability of the photoresist, which may cause deterioration of the shape of the photoresist pattern. The present invention has been made in view of the above circumstances, that is, to propose a novel compound suitable as an acid generator for a photoresist composition, an acid generator formed of the compound, a photoresist composition containing the acid generator, and A method of forming a photoresist pattern of the photoresist composition is used. The present inventors have proposed the following means for solving the above problems. That is, the first aspect of the present invention is a compound represented by the following formula (bl-3). [Chemical 1]

Wherein R41, R42 and R43 are each independently an alkyl group, an ethyl group, an alkoxy group, a carboxyl group, a hydroxyl group, or a hydroxyalkyl group; ... is an integer of 0 to 3, and is an integer of 〇~3, "为〇 An integer of ～2, wherein 'n, ri2 and n3 are not simultaneously 〇; X/ is an anion}. Further, the second aspect of the present invention is the above-mentioned -8-200821292 formula (b 1 -3) An acid generator formed by the compound shown. Further, the third aspect of the present invention is a photoresist composition which contains a change in alkali solubility due to an acid-based action. a photoresist composition of the substrate component (A) and an acid generator component (b) which generates an acid by exposure, characterized in that the acid generator component (B) is contained by the above formula (bl-3) The acid generator (B1) formed by the compound. φ Further, the fourth aspect of the present invention is a method for forming a photoresist pattern, which comprises the use of the third embodiment of the present invention described above. The step of forming a photoresist film on the substrate by the photoresist composition of the aspect and the step of exposing the photoresist film And the step of developing the photoresist film to form a photoresist pattern. Further, the term "structural unit" in the specification and the patent application refers to a monomer unit constituting a resin component (polymer) (m ο η 〇mer) Unit). • “Exposure” is a general tribute to radiation exposure. The "alkyl group" is a linear monovalent, branched chain, and cyclic monovalent saturated hydrocarbon group, unless otherwise specified. The "lower alkyl group" means an alkyl group having 1 to 5 carbon atoms. The "lower alkyl group" in the "halogenated lower alkyl group" also has the same meaning. The present invention provides a novel compound suitable as an acid generator for a photoresist composition, an acid generator formed of the compound, a photoresist composition containing the acid generator, and a photoresist having the photoresist composition. The method of forming the pattern. -9- 200821292 "Compound" The compound 'as a compound of the present invention' (asPect) is as shown in the above formula (bl-3). In the above formula (bl-3), R41, R42 and R43 are each independently an alkyl group, an ethyl group, an alkoxy group, a carboxyl group or a hydroxyalkyl group. In R42 and R43, the alkyl group is preferably a φ of a lower alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group, and a methyl group, an ethyl group, a propyl group or a different group. More preferably, propyl, η-butyl, tert-butyl. The alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a linear or branched chain alkoxy group, and most preferably a methoxy group or an ethoxy group. The hydroxyalkyl group is preferably a group obtained by substituting one or a plurality of hydrogen atoms of the above alkyl group with a hydroxyl group, for example, a methylol group, a hydroxyethyl group, a hydroxypropyl group or the like. 1^ is an integer of 0 to 3, preferably 1 or 2, more preferably 1. N2 is an integer of 0 to 3, preferably 0 or 1, more preferably 0. # n3 is an integer of 0 to 2, preferably 0 or 1, more preferably 1. Where ηι, 112 and 113 are not 0 at the same time. In the above formula (bl-3), X· is an anion. The anion portion of X_ is not particularly limited, and those known as an anion portion of the key salt acid generator can be suitably used. For example, an anion represented by the general formula "R14S03. (R14 is a linear, branched or cyclic alkyl group or a halogenated alkyl group)" can be used. In the above formula "R14SO", R14 is linear, Branched chain or cyclic alkyl or halogenated alkyl. -10- 200821292 The linear or branched alkyl group of R14 is preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 8, and most preferably a carbon number of 1 to 4. The cyclic alkyl group of R14 is preferably a carbon number of 4 to 15, more preferably a carbon number of 4 to 10, and most preferably a carbon number of 6 to 10. The above R14 is preferably a halogenated alkyl group. That is, in the above formula (bl-3), X· is preferably a halogenated alkylsulfonic acid ion. The halogenated alkyl group is one in which a part or all of the hydrogen atom in the alkyl group is replaced by a halogen atom. Here, the halogenated compound system is a halogen atom which may be substituted by a halogen atom in the case where the "alkyl group" in the above R14 is the same, such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. In the halogenated alkyl group, 50 to 100% of the total number of hydrogen atoms is preferably substituted by a halogen atom, and more preferably all of them are substituted. Among them, the halogenated alkyl group is preferably a linear, branched or cyclic fluorinated alkyl group. The linear or branched fluorinated alkyl group is preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 8, and most preferably a carbon number of 1 to 4. The cyclic fluorinated alkyl group is preferably a carbon number of 4 to 15, and more preferably a carbon number of 4 to 1 Å, and most preferably a carbon number of 6 to 10. Further, the fluorination rate of the fluorinated base (the ratio of the number of fluorine atoms substituted by fluorination to the total number of hydrogen atoms in the fluorinated group is the same as the following), preferably 10 to 100%, More preferably, it is 50 to 100%, and particularly preferably, the hydrogen atom is replaced by a fluorine atom, and the strength of the acid is preferably increased. In the above formula (bl-3), X· can be used in the following formula. (b_3) -11 - 200821292 An anion, an anion represented by the following formula (b-4), and the like. [Chemical 2]

•••(b-4) [wherein, X" is an alkylene group having 2 to 6 carbon atoms substituted with at least one hydrogen atom replaced by a fluorine atom; Y", Z" are each independently at least one hydrogen atom to be fluorine An atom-substituted alkyl group having 1 to 10 carbon atoms] In the formula (b-3), X" is a linear or branched alkyl group having at least one hydrogen atom substituted by a fluorine atom, and the alkyl group The carbon number is 2 to 6, preferably 3 to 5 carbon atoms, and most preferably carbon number 3. In the formula (b-4), Y" and Z" are each independently a linear or branched alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and the alkyl group has a carbon number of from 1 to 10, preferably. The carbon number is 1 to 7, and the most preferred carbon number is 1 to 3. When the carbon number of the alkyl group of X" or the carbon number of the alkyl group of Y" or Z" is in the above range, it is preferably as small as possible based on the solubility of the resist solvent, etc. Further, X" In the alkyl group of an alkyl group or a Y" or Z" group, the more the number of hydrogen atoms substituted by a fluorine atom, the stronger the strength of the acid, and the higher the energy light or the electron beam of 200 nm or less, It is better to improve transparency. The fluorination ratio in the alkylene group or the alkyl group is preferably from 70 to 100%, more preferably from 90 to 100%, most preferably a perfluoroalkylene group or a perfluoroalkyl group in which all hydrogen atoms are replaced by fluorine atoms. . -12- 200821292 A compound of the first aspect of the present invention is preferably shown below.

C3f7so; [Chemical 4]

-13- 200821292

C3F7SO3

C3F7SO3 is preferably a compound represented by the aforementioned chemical formulas (bl-31), (bl-34), 37), or (bl-40). <Production Method of Compound> The compound of the first aspect of the present invention, for example, can be represented by the following formula (bl-0-31) by the following formula (bl- The compound represented by 0-32) is used in a solvent such as copper benzoate in a solvent such as chlorobenzene or iodobenzene at a temperature of from 80 to 130 ° C for 100 to 12 (0.5 to 3 hours in TC, More preferably, it is 1 to 2 small and can be obtained. (b 1 - (b 1 - 3, with I ( II), better reaction - 14 - 200821292

[wherein R4M is the same as R41 in the above formula (b 1-3); ηι is the same as in the above formula (bl-3); X· is the same as above (b 1-3) X in the formula is the same content]

[wherein R42 and R43 are the same as those of R42 and R43 in the above formula (bl-3); and n2 and 113 are the same as those of n2 and 113 in the above formula (bl-3). Wherein ηι, n2 and n3 are not simultaneously 〇] ° "acid generator" The acid generator of the second embodiment of the present invention (hereinafter also referred to as acid generator (B 1 )), It is formed of the compound represented by the above formula (b 1-3). Wherein R41, R42 and R43; ηι, n2 and n3 -15-200821292; and X are the same as those enumerated in the above-mentioned first embodiment of the present invention. <<Photoresist composition>> The photoresist composition of the third aspect of the present invention is a substrate component (A) containing a change in alkali solubility based on an acid action (hereinafter, also referred to as ( A) component) and an acid generator component (B) (hereinafter, also referred to as component (B)) which generates an acid by exposure, and the component (B) is a compound represented by the above formula (bl-3) The acid generator (B1) formed. In the resist composition of the present invention, as the component (A), a polymer material which changes the solubility of the alkali by the action of an acid can be used, and a low molecular material which changes the solubility of the alkali by the action of an acid can also be used. Further, the photoresist composition of the present invention may be a negative photoresist composition or a positive photoresist composition. • In the case where the photoresist composition of the present invention is a negative photoresist composition, for example, the component (A) is an alkali-soluble resin, and the negative-type photoresist composition is added with a crosslinking agent (C). In the negative resist composition, when an acid is generated in the component (B) by exposure when the photoresist pattern is formed, the exposed portion causes a cross between the alkali-soluble resin and the crosslinking agent via the action of the acid. And a change to an alkali-insoluble sulphonic acid-soluble resin, which is derived using at least 1 -16-200821292 selected from lower alkyl esters of α-(hydroxyalkyl)acrylic acid or α-(hydroxyalkyl)acrylic acid. The resin of the unit is preferably formed to form a good photoresist pattern having a lower swelling. Further, α-(hydroxyalkyl)acrylic acid means an acrylic acid having a carbon atom bonded to a hydrogen atom at the α-position of a carboxyl group, and a hydroxyalkyl group bonded to a carbon atom of the α-position (preferably having a carbon number of 1 to 5) One or both of the hydroxyalkyl) a-hydroxyalkylacrylic acids. The crosslinking agent (C) is, for example, usually an amine-based crosslinking agent such as glycoluril having a methylol group or an alkoxymethyl group, which can form a good photoresist pattern having a lower swelling property. Preferably. The amount of the crosslinking agent (C) to be added is preferably from 1 to 50 parts by mass based on 100 parts by mass of the alkali-soluble resin. The photoresist composition of the present invention is a positive resist composition, and the component (A) is an alkali-insoluble component having an acid-dissociable dissolution inhibiting group. When the photoresist pattern is formed, an acid is generated by the (B) component by exposure, and the acid dissociable dissolution inhibiting group is dissociated by the action of the acid to change the (A) component to alkali solubility. Therefore, in the formation of the photoresist pattern, when the photoresist film obtained by applying the positive-type photoresist composition on the substrate is subjected to selective Φ exposure, the exposed portion is converted to alkali solubility, and is not exposed. The portion is still in an alkali-insoluble, unaltered state, and can be subjected to alkali development. In the photoresist composition of the present invention, the component (A) is preferably a component which increases alkali solubility based on the action of an acid, and a resin component (A1) which increases alkali solubility based on the action of an acid (hereinafter, Also known as (A1) component) is better. That is, the photoresist composition of the present invention is preferably a positive photoresist composition. Further, the photoresist composition of the present invention is preferably used as a photoresist composition for immersion exposure in a method for forming a photoresist pattern containing an immersion exposure step, and further comprises a photoresist layer formed of three layers. In the method of forming the photoresist pattern of the step -17 - 200821292, it can be suitably used as a positive photoresist composition for forming an upper photoresist film. Next, in the method for forming a photoresist pattern including the step of immersion exposure and/or the step of forming a three-layer photoresist layer, an example of the (A 1 ) component which is more suitable as a positive photoresist composition will be exemplified. . &lt; (A1) component&gt; @ The component (A 1 ) which is preferably used in the positive resist composition is preferably a structural unit (a 1 ) derived from an acrylate having an acid dissociable dissolution inhibiting group. . Further, the component (A1) is preferably a structural unit (a2) derived from an acrylate having a cyclic group containing a lactone. Further, the component (A1) is preferably a structural unit (a3) derived from an acrylate further having an aliphatic hydrocarbon group having a polar group. In the specification and the scope of the patent application, "the structural unit derived from the acrylate" means the structural unit constituted by the cracking of the ethylenic double bond of the acrylate. The "acrylate" means a carbon atom of the α-position, in addition to an acrylate having a hydrogen atom bonded thereto, and a compound in which a carbon atom at the α-position is bonded with a substituent (atom or a group other than a hydrogen atom). The substituent is, for example, a halogen atom, a lower alkyl group, a halogenated lower alkyl group or the like. A halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like is preferable, particularly preferably a fluorine atom. "halogenated lower-grade hospital base", for example, a base obtained by substituting at least one or all hydrogen atoms of the above-mentioned lower-grade yard base with the above-mentioned halogen atom, and the α-position of the structural unit derived from the acrylate (the carbon atom of the alpha position) And, unless otherwise specified, means a carbon atom bonded to a carbonyl group. In the acrylate, a lower alkyl group of the substituent at the α-position, specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an η-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isoprene group A linear or branched chain lower alkyl group such as a benzyl group or a neopentyl group. • In the present invention, the α-position of the acrylate is bonded with a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group, and a hydrogen atom, a fluorine atom, a lower alkyl group or a halogenated lower alkyl group. More preferably, a hydrogen atom, a fluorine atom, a lower alkyl group or a fluorinated lower alkyl group is more preferable, and it is industrially easy to obtain, and a hydrogen atom or a methyl group is most preferable. • Structural unit (a 1 ) The structural unit (al ) is a structural unit derived from an acrylic acid ester containing an acid dissociative dissolution inhibiting group. The acid dissociable dissolution inhibiting group in the structural unit (al) is such that, as long as the (A 1 ) component has an alkali-insoluble alkali dissolution inhibiting property before dissociation, the entire component (A1) is changed to alkali solubility after dissociation. In other words, it is possible to use an acid dissociable dissolution inhibiting group which has been proposed as a base resin for enhancing a chemical type resist composition. In general, for example, a carboxyl group in (meth)acrylic acid may form a cyclic or chain tertiary alkyl ester group, or an acetal acid dissociable dissolution inhibiting group such as an alkoxyalkyl group. Further, "(meth)acrylic acid" means one or both of acrylic acid and methacrylic acid. Here, the "trialkyl ester", for example, a hydrogen atom of a carboxyl group is substituted with a chain or a cyclic alkyl group to form an ester, and an oxygen atom at the terminal of the carbonyloxy group (-C(o)-o-), a bond A structure obtained by the tertiary carbon atom of the above-mentioned chain or cyclic alkyl group. In the above tertiary alkyl ester, the bond between the oxygen atom and the tertiary carbon atom can be interrupted by the action of an acid. Further, the aforementioned chain or cyclic alkyl group may have a substituent. _ Hereinafter, the acid-dissociable group composed of a carboxyl group and a tertiary alkyl ester is conveniently referred to as a "tri-terminated alkyl ester type acid dissociable dissolution inhibiting group". The tertiary alkyl ester type acid dissociable dissolution inhibiting group, for example, an aliphatic branched chain acid dissociable dissolution inhibiting group, an acid dissociable dissolution inhibiting group containing an aliphatic cyclic group, and the like. Here, the term "aliphatic" as used in the scope of the patent application and the specification refers to the relative complication with respect to aromatics, that is, it is defined as a group or a compound having no aromaticity. The "aliphatic branched chain" means a branched chain structure having no aromaticity. The structure of the "aliphatic branched chain acid dissociable dissolution inhibiting group" is not limited to a group (hydrocarbon group) formed of carbon and hydrogen, but a hydrocarbon group is preferred. Further, the "hydrocarbon group" may be either saturated or unsaturated, and it is generally preferred to saturate. The aliphatic branched chain acid dissociable dissolution inhibiting group is preferably a C 4 to 8 tertiary alkyl group, specifically, for example, tert-butyl, tert-pentyl-20-200821292, tert-heptyl or the like. The "aliphatic cyclic group" means a monocyclic or polycyclic group having no aromaticity. The "aliphatic cyclic group" in the structural unit (al) may have a substituent or may not have a substituent. The substituent is, for example, a lower alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated lower alkyl group having 1 to 5 carbon atoms substituted by a fluorine atom, an oxygen atom (=0) or the like. • The basic ring structure of the substituent is removed from the "aliphatic cyclic group", and the group (hydrocarbon group) composed of carbon and hydrogen is not limited, but a hydrocarbon group is preferred. Further, the "hydrocarbon group" may be either saturated or unsaturated, and generally it is preferably saturated. The "aliphatic cyclic group" is preferably a polycyclic group. Specific examples of the aliphatic cyclic group may be, for example, a lower alkyl group, a fluorine atom or a fluorinated alkyl group, or a monocyclic alkane, a bicycloalkane or a tricycloalkane which may be unsubstituted. A group obtained by removing one or more hydrogen atoms from a polycyclic alkane such as a tetracycloalkane. Specifically, for example, it is removed by a monocycloalkane such as cyclopentane or cyclohexane or a polycyclic alkane such as adamantane, raw spinane, isopentane, tricyclodecane or tetracyclododecane. A group obtained by one or more hydrogen atoms. Further, the acid dissociable dissolution inhibiting group containing an aliphatic cyclic group, for example, a group having a tertiary carbon atom in a ring skeleton of a cyclic alkyl group, etc., specifically, for example, 2-methyl-2-anomantane Base, or 2-ethyl-2- 2 adamantyl and the like. Or, for example, in the structural unit represented by the following formula (al), an aliphatic ring group such as an adamantyl group is bonded to a group of an oxygen atom of a carbonyloxy group (_C(0)-0-), and a group having a branched chain alkyl group having a tertiary carbon atom bonded thereto, etc. -21 - 200821292 [Chem. 8]

[In the formula, R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group; and R15 and R16 are an alkyl group (may be a linear chain or a branched chain, preferably a carbon number of 1 to 5). The halogen atom, lower alkyl group or halogenated lower alkyl group of R in the above formula is, for example, the same as the halogen atom, lower alkyl group or halogenated lower alkyl group which may be bonded to the α-position of the above acrylate. The "acetal type acid dissociable dissolution inhibiting group" is generally an oxygen atom bonded to a hydrogen atom at the terminal of an alkali-soluble group such as a carboxyl group or a hydroxyl group. Therefore, when an acid is generated by exposure, the bond between the acetal type acid dissociable dissolution inhibiting group and the oxygen atom to which the acetal type acid dissociable dissolution inhibiting group is bonded is cut by the action of the acid. The acetal type acid dissociable dissolution inhibiting group is, for example, a group which is not represented by the following formula (ρ 1 ). -22- 200821292 [c 9] [c1] (p1) [wherein, R1', R2' are each independently a hydrogen atom or a lower alkyl group, η is an integer of 0 to 3, and Υ is a lower alkyl group or An aliphatic cyclic group] # In the above formula, η is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 〇. The lower alkyl group of R1' and R2' is, for example, the same as the lower alkyl group of the above R, and preferably a methyl group or an ethyl group, and a methyl group is most preferable. In the present invention, it is preferred that at least one of R1' and R2' is a hydrogen atom. Namely, the acid dissociable dissolution inhibiting group (Ρ 1 ) is preferably a group represented by the following formula (Ρ 1-1 ). [γ10] • γ ——g—°~(CH2)—*Υ Η π · · (pi ι) [wherein, R1', η, lanthanide and R1' in the above formula (pi), The contents of η and Υ are the same content. The lower alkyl group of hydrazine is, for example, the same as the lower alkyl group of the above R. The aliphatic ring group of hydrazine can be appropriately selected, for example, from the above-mentioned one-ring or polycyclic aliphatic ring group, which is conventionally used in ArF photoresist, etc., -23-200821292, for example, as described above. The aliphatic cyclic group is the same content. Further, the acetal type acid dissociable dissolution inhibiting group is, for example, a group represented by the following formula (P2). R17 ——C—Ο—R19 • R18 -&quot;(p2) [wherein, R17 and R18 are each independently a linear or branched alkyl group or a hydrogen atom, and R19 is a linear chain. a branched or cyclic alkyl group, or R17 and R19 are each independently a linear or branched alkyl group, and the end of R17 is bonded to the end of Ri 9 to form a ring] R17, R18, alkane The carbon number of the group is preferably from 1 to 15, which may be a linear or branched chain, preferably an ethyl group or a methyl group, and a methyl group being the most preferred. In particular, it is preferred that either of R17 and R18 is a hydrogen atom and the other is a methyl group. When R19 is a linear, branched or cyclic alkyl group, the number of carbon atoms is preferably from 1 to 15, and it may be any of a linear chain, a branched chain or a cyclic group. When R19 is a linear or branched chain, the carbon number is preferably from 1 to 5, more preferably ethyl or methyl, and most preferably ethyl. When R19 is a ring, it is preferably 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, it can be substituted by a fluorogenic-24-200821292 or a fluorinated compound, or a monocyclic alkane, a bicyclic chain, a tricyclic chain, a tetracyclic alkane, or the like. The base of one or more hydrogen atoms is removed from the alkane. Specifically, 'for example, a monocyclic alkane such as cyclopentane or cyclohexane, or one or more polycyclic alkane such as adamantane, raw spinane, isopentane, tricyclodecane or tetracyclododecane is removed. The base of a hydrogen atom, etc. Among them, a group obtained by removing one or more hydrogen atoms from adamantane is preferred. Further, in the above formula, R17 and R19 are each independently a linear or φ-branched alkylene group (preferably an alkylene group having 1 to 5 carbon atoms), and the end of R19 may be bonded to the end of R17. Bonding is also possible. At this time, R17 and R19 are bonded to the oxygen atom bonded to R19, and the oxygen atom forms a cyclic group with the carbon atom bonded to R17. The ring base is preferably a 4 to 7 member ring, and a 4 to 6 member ring is preferred. Specific examples of the cyclic group include, for example, a tetrahydropyranyl group, a tetrahydrofuranyl group and the like. r structural unit (al) selected by using Φ selected from the structural unit represented by the following general formula (al-0-1) and the structural unit represented by the following general formula (al-0-2) More than one type is preferred. [化 12]

[In the formula, R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower-grade courtyard; X1 is an acid-dissociable dissolution-inhibiting group] -25- 200821292

Ο

(al — 0-2) [wherein R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group; X2 is an acid dissociable dissolution inhibiting group; Y2 is an alkylene group or an aliphatic cyclic group] In the formula (al-0-1), the halogen atom, the lower alkyl group or the halogenated lower alkyl group of R is the same as the above-mentioned halogen atom bonded to the α-position of the acrylate, lower alkyl group or halogenated lower alkyl group. content. X1 is not particularly limited as long as it is an acid dissociable dissolution inhibiting group, and may be, for example, the above-mentioned tertiary alkyl ester type acid dissociable dissolution inhibiting group or acetal type acid dissociating dissolution inhibiting group, and tridecane. The ester-type acid dissociable dissolution inhibiting group is preferred. In the formula (al-0-2), R has the same content as R in the above formula (al-0-1). X2 is the same as X1 in the formula (al-0-1). Y2 is preferably an alkylene group having 1 to 4 carbon atoms or a divalent aliphatic cyclic group. In the case of the aliphatic cyclic group, the same as the above-mentioned "aliphatic cyclic group" can be used, except for the use of a group in which two or more hydrogen atoms are removed. In the structural unit (al), more specifically, for example, a structural unit represented by the following general formulae (al-Ι) to (al-4). [Chem. 14]

(a1 - 1) (al -2) (a1 - 3) (a1 - 4)

[In the above formula, X' is a tertiary alkyl ester type acid dissociable dissolution inhibiting group; γ is a lower alkyl group having 1 to 5 carbon atoms, or an aliphatic cyclic group; η is an integer of 〇 to 3; m is 0 or 1; R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower-grade courtyard; R1 and r2 are each a hydrogen atom or a lower-order courtyard having a carbon number of 1 to 5] The above formula (al-Ι) to ( The R' system in al-4) is the same as R in the formula (al_ 0-1 ) to (al-〇-2). -27-200821292 Preferably, at least one of the above R1' is a hydrogen atom, and more preferably a hydrogen atom. η is preferably 0 or 1. The content of X' is the same as the cyclic tertiary alkyl ester type acid dissociable dissolution inhibiting group exemplified in the above X1. The aliphatic cyclic group of hydrazine is, for example, the same as those exemplified in the description of the above "aliphatic cyclic group". The following are specific examples of the structural unit φ represented by the above formulas (al-Ι) to (al-4).

-28- 200821292 [Chem. 15]

(a 1-1 -1) (a1*&quot;1~2) (al-1-3)

-ch2

(CH2)3CH3

(a1-1-8)

(at-1-9) (at-1-7)

(a1 -1 to 10)

CH

(a1-1-14) (a1-1-15)

(a1-1-16) -29- 200821292 [Chem. 16]

(a1-1-19) •CH2—CH^— 0=^ 9H3 χκ&gt; (at-t-20) ϋΜ3 I - CH2—C-^- —^CH2—CH^ 4CH2-y Ten °4^t

—^CH2一CH^- 0=^ C2H5 V) °tD (al-1- 22) (a1-t-23) (at-1-24) ch3 -^ch2~c »2一u 丁^CH2~ CH^— °\ ?HyCH3 0 gas science, CH3| ch3 (at-1-25)

Ch3 (a1-1-26) -«^CH2—CH^* CH3 0=1 CH3 -ch2—chV i f · b 〇==\ CH:o

(a1 -1 to 27)

Ch3 •CH “〒10=^ ?H3/CH3 〇, 乂CH -ch2—c+ 〇=J,,h3 (a1 -1 -28> CH3 ch2—?hV —^ch2—order + ° V ?2H§ 〇=\^ C2H5

(a1-1-29) b6 °6 b (a1-1-30) (a1 -1-31) (at-1-32) -30- 200821292 [Chemistry 17] 9H3 ch3 ten ch2-c+·

Ch3 〇η3 _CH2—jcH2— --- Q

H3c (a1+33) ch3 ch3 〇H c2h5

(at-1-34) (a1-Bu 35) (a 1-1-36) -^ch2—c 0=l ?h3 o

, 2jcT 〇=\ c2h5°6 't&gt; ch2—ch}. =\ (?2Hs -CH2—CH^ °=l ?h3

(al -1-37) (a1-t-38) (a 1-1-39) (al-1-40) ch2^h)- ^ch2^-)- ^ch2-c^ -^ch2^h )-

H3ct wood, CH3 H3C&quot;j^CH3 H3G-ch3 CH3 O, CH3 H3(T C2H5 o ch3 C2H5 (a1-1-42) (a1 -1-43) (al-1-44) (a1 -1-45 ) [Chem. 18]

(a 1-2-1) -^ch广ch} Cal-2-2) CHj [CH2-j 孓 (a1 - 2-3) °4 〇

(a 1-2-4)

Ten H2—ch)·°4 〇·

(a1-2-6) (a 1-2-5) -31 - 200821292 [Chem. 19]

—^CH2&quot;&quot;|Hh —(〇Η2-〇4* 〇Jl 〇=\ 〇〇=\〇XJO) (al^XKD 0, ,c (a 1-2-7) -(ch2-ch) - 〇4 ( 〇^^ (a1-2-10) ch3 —(ch2-c4-〇4 (a1-2-13) ^(ch2-ch)-04 (a 卜 2-16) —^ch2-c ·)— 〇. (at-2-19) (a 1-2*8) ch3 (at-2-9) CH2-cf- &quot;fcH2-W 卜. 4- cf3 (al-2-12) CH3 —^ch2~c*)- (a1-2-15) cf3

.0 p

0 -fcH2-C-)- —(CH2-C-10°子-{〇Λ ° ^ (at-2-17) (at-2-20) Λ 〇, (a1-2-18) (a1- 2-2t) 200821292 [Chem. 20] CH3 —(ch2-c^— 0, (at-2-22) ΓΌ -{ch2-ch)-〇4 ~{ch2- ch3 1 V c- -f〇H2 — CH\ .4) (a1-2-25) (al-2-23) ch3;=f (al ten 26&gt; -(ch2-

; O 〇 a (a1-2- 24) - (ch2^h)- Ό 〇 t. (a1-2- 28&gt;T&gt; one 丫Λ (al-2-32) ί ) —(ch2

(al-2 - 29) cf3

0, (at-2-30) Γ Ten H2-order-°4 (a1-2-3t) (a1-2-33) CHj ch3 [ch2-c-)— -{ch2-c4· Take one. jO o - (a 1 -2-34) (a 1 —2—35)

•o^O -33- 200821292 [Chem. 21]

(al-2-39) (a1-2-40) (a b 2-41)

(a1-2-42) (a1-2-43)

- 34- 200821292 [化22] ch3 ch3 十 CH2-i 子 十 -^CH2-CH^ 0 p ° ο p

o y=o Q O

o

0

H3C© C2H® H3&quot; (at-3-t) (a 1-3-2) (a1 -3 - 3)

(a1 -3 - 9) (a1-3H0) (a1-3 -11) (a Bu 3 -12) H3〇H3Cb c2Hs3q -35- 200821292 [Chem. 23]

Ch3 ch3 —AcH2~C^ ^CH2-C-^- —^CH2~CH^· —^-CH2-CHj- 〇=l o===\ O1^ Ο Ο p O

o

o

o

o o o o 5i〇 H3ciy czH5iy H3ctu Ah (al - 3-13) (a1 -3-14) (a1-3H5) (a1-3-t6) •CH2 - CH+°4 o •ch2-〒+ 〇=l

,ch2

o

o c2h5

(a1 domain 3-20) ch3 ch3 ten CH2_i+ ten CH2j ten-^CH2-CHj- -^CH2-CH^ 〇 b 〇 〇 , ° p

o h3c-

(a1 - 3-21)

O :3⁄4) CzH5-3〇 ^3〇^\ , C2H5- (a1-3-23) (a1-3-24) -36- 200821292 [Chem. 24] CH CH3 c

o o . gas.

o i i. . k factory oooooo (a1-4-1) (a 1-4-2) (at-4-3) (a 1-4-4) te (a 1-4-5) ten called ten (-ch2 —ch)— ch3 〇〇4〇0=\ -fCH2_chWm 4 4 h

O

O

O o (at-4-6)

Q

O _ XD 〇 (al 4 7) (a1-4-8) (a 1-4*9) CH3 (at-4-10) ?H3 〇ζ o°&gt;

(at-4-1t) (a1-4-12)

V

O o (at-4-13) (al-4-14) &gt; o (a 1-4 -15) -37- 200821292 [Chemical 25] CH2, c-leaf H24 word ten°\ 〇=o °〇 ° P corpse

o&gt; o

o &gt;=〇 o ) Q

O

〇; O ^=0 1 =〇Q d (a1-4-16) CH3 )© (at-4-17) to ^ (a1-4-18) (a 1-4-19)

O O

O O

o (at -4-20) ch3 H〇-^

o o 〇No -(ch2-ch|. ^ch2-c^ -^ch2^ch)- ^ch2-c|·

0

0 )=0 &gt;=0 O 0 Ok °v o

o o o&gt; o

·〇

o (at-4-26) (at-4-27) (a1-4-28) (a1-4-29) (a1-4-30) -38- 200821292 Structural unit (al), can be used alone 1 Alternatively, two or more types may be used in combination. Among them, the structural unit represented by the general formula (a 1 -1 ) is preferred. Specifically, it is selected by using a structural unit represented by the formula (a 1 -1 - 〇 to (a 1 -1 -6 ) or the formula (a 1 -1- 3 5 ) to (al-1-41) At least one of them is optimal. Further, the structural unit (al) is specifically a formula (a 1 -1 - which is a structural unit containing the formula (al-1-l) to the formula (a 1 -1 - 4 ) 0 1 ) The unit shown, or the following formula (al-1-02) containing structural units of the formula (al-1-35) to (al-1-41) is preferred. [Chem. 26]

[wherein R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group, and R11 is a lower alkyl group] -39- 200821292

2 oR1 r (〇h2)h \-/--.(31-1-02) [wherein R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group, and R12 is a lower alkyl group, and h is In the formula (al-1-Ol), R has the same content as R of the above formula (al-Ι). The lower alkyl group of R11 is the same as the lower alkyl group represented by R, and a methyl group or an ethyl group is preferred. In the formula (al-1-02), R has the same content as R of the above formula (al-Ι). The lower alkyl group of R12 is the same as the lower alkyl group represented by R, and is preferably a methyl group or an ethyl group, and preferably an ethyl group. h is preferably 1 or 2, and 2 is the best. • The ratio of the structural unit (al) in the (A1) component is preferably from 1 to 80 mol%, and from 20 to 70 mol%, for the entire structural unit of the composition (.A1). Good, 25 to 50 mol% is the best. When it is at least the lower limit 値, it is easy to form a pattern when it is a positive resist composition, and it can be balanced with other structural units when it is below the upper limit 値. Structural unit (a2) -40- 200821292 In the present invention, the component (A1) is preferably a unit (a2) further comprising an acrylate having a lactone-containing cyclic group in addition to the above structural unit. Wherein, the cyclic group containing a lactone is a cyclic group containing a -O-C(O)-ring. The lactone ring is used as a ring unit. The lactone ring is a monocyclic group. If the ring has other ring structures, it is called a polycyclic group. The lactone ring-containing group of the structural unit (a2) can effectively improve the photoresist film property and improve the hydrophilicity in the case of forming a photoresist film, so that it is effective for improving the developer liquid. By. Among them, the structural unit (a2) has no unit defined by any. Specifically, a monocyclic group containing a lactone, for example, a group obtained by r to 1 hydrogen atom, or the like. Further, a polycyclic ring containing a lactone has a lactide ring, a tricycloalkane, a tetracycloalkane atom, and the like. In the example of the structural unit (a2), more specifically, the structural unit represented by the formula (a2-l) to (a2-5) and the like. One count of the structural structure derived from (al) is only the constitutional time, and any butyrolactone removal group may be used regardless of the close affinity of the (A1) component to the substrate, for example, by removing one hydrogen, for example, the following -41 - 200821292 [化28]

® [wherein R is a hydrogen atom, a halogen atom, a lower-grade or a halogenated lower-grade, R, each independently a hydrogen atom, a lower alkyl group, or an alkoxy group having 1 to 5 carbon atoms, and m is 0 or 1 An integer, A is an alkylene group or an oxygen atom having a carbon number of 1 to 5] In the formula (a2-l) to (a2-5), 'R has the formula (a 1 ) with the above structural unit (a 1 ) R in the same content. R, a lower alkyl group having the same content as the lower alkyl group of R in the above structural unit (a 1 ), a C alkyl group having 1 to 5 carbon atoms, Specifically, for example, methyl group, ethyl group, η-propyl group, iso-propyl group, etc., in the formula (a2-l) to (a2-5), R, industrially easy to obtain, etc. In view of the above, a hydrogen atom is preferred. The following are examples of specific structural units of the above general formulae (a2-l) to (a2-5). -42- 200821292 [Chem. 29]

(a244&gt; (a2-1-5) (a24-6)

-43- 200821292 [Chem. 30]

4

(32-2-5) 〇 ch3 ^CH2-C&gt;- -{cH2-CHf 40===^ Ο,

Ο CH3

(a2-2-6)

(a2-2-8) (32-2.7)

(32-2-9) O (a2-2-10) -44- 200821292 [Chem. 31]

CH3 4ch2-chV. 4

(a2-3-7) (a2-3-8)

(a2-3-10) -45 200821292 [Chem. 32]

(a2-4-11) (a2-4-12) -46- 200821292 [Chem. 33]

Wherein, it is preferred to use at least one selected from the general formulae (a2-l) to (a2-5), and at least one selected from the general formulae (a2-l) to (a2-3). Kind to be better. Specifically, the chemical formulas (a2-1-1), (a2-l-2), (a2-2-l), (a2-2-2), (a2-3-l), (a2) are used. One or more selected from -3-2) and (a2-3-9) and (a2-3-10) are preferred. In the component (A1), the structural unit (a2) may be used singly or in combination of two or more. -47- 200821292 (A 1 ) The proportion of the structural unit (a2) in the composition is preferably 5 to 60 mol%, and 10 to 50 mol%, based on the total of the structural units constituting the component (A1). Preferably, it is preferably from 2 to 50 mol%. When the lower limit is 値 or more, the effect can be sufficiently obtained when the structural unit (a2) is contained, and the balance with other structural units can be obtained when the upper limit is less than 値. • Structural unit (a3) In the present invention, the component (A1) contains, in addition to the structural unit (a) or the structural units (al) and (a2), a (a3) aliphatic group having a polar group. The structural unit derived from the hydrocarbon group acrylate is preferred. When the structural unit (a3) is contained, the hydrophilicity of the (A1) component can be improved, and the affinity with the developer can be improved, thereby improving the alkali solubility of the exposed portion. It is expected that the resolution is improved. A polar group such as a hydroxy group in which at least one hydrogen atom of a hydroxyl group, a cyano group, a carboxyl group or an alkyl group is substituted by a fluorine atom (hereinafter also referred to as "fluorinated alkyl alcohol") The hydroxy group is preferably an aliphatic hydrocarbon group such as a linear or branched hydrocarbon group having 1 to 10 carbon atoms (preferably an alkylene group) or a polycyclic aliphatic hydrocarbon group (polycyclic group). A polycyclic group, for example, a resin which can be used for a photoresist composition for an ArF excimer laser, which is appropriately selected from the contents of most proposals, wherein it contains at least a hydroxyl group, a cyano group, a carboxyl group, or an alkyl group. a hydroxyalkyl group in which a hydrogen atom is replaced by a fluorine atom More preferably, the structural unit derived from the aliphatic polycyclic acrylate is one or more hydrogen atoms removed by a polycyclic group, for example, a dicycloalkane, a tricycloalkane or a tetracyclic alkane. - 200821292 The base to be obtained, etc. Specifically, for example, a group obtained by removing one or more hydrogen atoms from a polycyclic alkane such as adamantane, raw spinane, isopentane, tricyclodecane or tetracyclododecane In the polycyclic group, it is more suitable for the industry to remove two or more hydrogen atoms from adamantane, to remove two or more hydrogen atoms from the original spinel, and to remove two or more hydrogen atoms from tetracyclododecane. In the structural unit (a3), when the hydrocarbon group in the aliphatic hydrocarbon group containing a polar group is a linear or branched hydrocarbon group having a carbon number of 1 to 1, a hydroxyethyl ester derived from a propenic acid The structural unit is preferably, and when the hydrocarbon group is a polycyclic group, for example, a structural unit represented by the following formula (a3_1), a structural unit represented by (a3-2), a structural unit represented by (a3 - 3), or the like is preferable. 34]

ΟΗ (a3-3) [wherein R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group, j is an integer of 1 to 3, k is an integer of 1 to 3, and t' is 1 to 3 An integer, 1 is an integer from 1 to 5, and s is an integer from 1 to 3) wherein R in the formula (a3 -1 ) to (a3 -3 ) is a halogen atom, a lower alkyl group or a halogenated lower alkyl group, and the above The 200821292 halogen atom, lower alkyl group or halogenated lower alkyl group which may be bonded to the acrylate is the same. In the formula (a3-l), it is preferable that j is 1 or 2, and 1 is more preferable. In the case where j is 2, it is more preferable that the hydroxyl group is bonded to the 3 and 5 positions of the adamantyl group. In the case where j is 1, it is particularly preferable that the hydroxyl group is bonded to the 3 position of the adamantyl group. Among them, it is preferable that j is one, and it is particularly preferable that the hydroxyl group is bonded to three of adamantyl H. In the formula (a3-2), it is preferred that k is one. Further, it is preferred that the cyano group is bonded to the 5- or 6-position of the original spinnyl group. In the formula ("-3), it is preferred that t' is 1 and 1 is preferred, and s is preferably 1. The terminal of the carboxyl group of the acrylic acid is bonded to 2-originyl or 3 - a compound of the original spinel group is preferred. The fluorinated alkyl alcohol is preferably bonded to the 5 or 6 position of the original spinnyl group. Among the components (A1), the structural unit (a3) may be used alone, or • Two or more types may be used in combination. The ratio of the structural unit (a3) in the component (A 1 ) is preferably from 5 to 50 mol%, based on the total structural unit of the component (A1). 5 to 40 mol% is more preferable, and 5 to 25 mol% is most preferable. When the lower limit is _ 値 or more, the effect of containing the structural unit (a3) can be sufficiently obtained, and when the upper limit is less than 値, other structures can be obtained. Unit balance. • Structural unit (a4) (A 1 ) component, in the range that does not impair the effects of the present invention, may contain other structural units other than the above structural units (al) to (a3). (a4) ° The structural unit (a4) is not particularly limited as long as it is a structural unit not classified into the above structural units (al) to (a3). ArF can be used. A plurality of conventionally known structural units used for resistive compositions such as molecular lasers and KrF excimer lasers (preferably for ArF excimer lasers). The structural unit (a4), for example, contains non-acid dissociable The structural unit derived from the aliphatic polycyclic acrylate is preferably the same. The polycyclic group is, for example, the same exemplified as the structural unit (a 1 ) described above, and an ArF excimer laser can be used. A plurality of conventionally known structural units used for the resin component of a photoresist composition such as KrF excimer laser (preferably for ArF excimer laser), especially tricyclodecylalkyl, adamantyl, When at least one selected from the group consisting of tetracyclododecyl, iso-spinylalkyl and ortho-alkylidene is industrially preferable, the polycyclic group may be a straight carbon number of 1 to 5. The alkyl group may be substituted by a chain or a branched chain. The structural unit (a4), specifically, for example, a structural unit represented by the following general formulae (a4-l) to (a4-5), etc. -51 - 200821292 [ 35]

Wherein R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group; and a halogen atom, a lower alkyl group or a halogenated lower alkyl group of R in the formula (a4-1) to (a4-5) The above-mentioned halogen atom, lower alkyl group or halogenated lower alkyl group which may be bonded to the α-position of the acrylate is the same. When the structural unit (a4) is contained in the (human 1) component, the ratio of the structural unit () to the total φ position of the entire structure constituting the component (A1) is 1 to 30 mol%. Preferably, it is preferably more than 10% to 20% by mole. In the present invention, the component (A1) is a resin component (polymer) which is increased in solubility based on the action of an acid, and is suitable as a unit of the resin component (polymerization), for example, having a structural unit (a), a structural unit. a copolymer of (a2) and a structural unit (a3), the copolymer, for example, a copolymer obtained from structural units (al), (a2), and (a3), structural units (al), (a2), Copolymers obtained by (a3) and (a4). In the present invention, the component (A) is particularly preferably a copolymer (a 1 -1 ) containing a combination of structural units represented by the following formula (-52-200821292 A 1 -1 ). [化36]

D D

[In the formula, R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group. R2G is a lower alkyl group. In the formula (A 1 -1 ), the halogen atom, lower alkyl group or halogenated lower alkyl group of R is the same as the above-mentioned halogen atom, lower alkyl group or halogenated lower alkyl group which may be bonded to the α position of the acrylate. The content. Among them, R is preferably a hydrogen atom or a methyl group. #r2G is a lower alkyl group in which a methyl group or an ethyl group is preferred, and a methyl group is preferred. In the component (A), the copolymer (A1-1) may be used singly or in combination of two or more. The content of the copolymer (A1-1) in the component (A) is preferably 70% by mass or more, more preferably 80% by mass or more, and most preferably 100% by mass. When the lower limit of the range is 値 or more, when the composition is a positive resist, the lithography etch characteristics can be further improved. (A1) component, for example, a monomer derived from each structural unit, -53-200821292, for example, a radical polymerization initiator such as azobisisobutyronitrile (AIBN) can be produced by a polymerization reaction such as radical polymerization. Got it. Further, in the above-mentioned polymerization, the component (A1) may be, for example, a chain transfer agent such as HS-CH2-CH2-CH2-C(CF3)2-〇H, and -C(CF3)2- may be introduced at the end. OH group. Thus, a copolymer in which at least one hydrogen atom having an alkyl group substituted with a fluorine atom is introduced can be obtained, thereby effectively reducing defects or reducing LER (Line Edge Roughness: unevenness of the line side wall) effect. The mass average molecular weight (Mw) of the component (A1) (the polystyrene equivalent amount of the condensed penetrant chromatography method) is not particularly limited, and is generally preferably 2,000 to 50,000, more preferably 3,000 to 30,000, and 5,000 to 20,00 is the best. When it is less than the upper limit of the range, sufficient solubility is obtained for the photoresist as a photoresist, and when it is larger than the lower limit of the range, a good dry etching resistance or a resist pattern cross-sectional shape can be obtained. Further, the degree of dispersion (Mw/Mn) is preferably in the range of 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.2 to 2.5. Further, Μη is a number average molecular weight. Further, as the component (A1), the alkali-soluble resin component other than the copolymer (A1 -1), for example, another polymer compound used in the conventional positive-type photoresist composition can be used. In the positive resist composition of the present invention, the content of the (A 1 ) component can be appropriately adjusted in accordance with the thickness of the photoresist film to be formed. &lt;(B) Component&gt; -54- 200821292 In the photoresist composition of the present invention, the component (B) is an acid generator (B 1 ) formed by containing the compound represented by the above formula (b 1-3) ( Hereinafter, also referred to as (B1) component. In the formula, R41, R42 and R43; ηι, n2 and n3; X_ are the same as those enumerated in the above-mentioned first aspect of the present invention. (B) component, because it contains the (B 1 ) component, it has good properties for general resist solvents such as propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), and ethyl lactate (EL). Therefore, in the method of forming a resist pattern containing an immersion exposure step or a step of forming a three-layer photoresist layer, it is used as a resist composition for immersion exposure or as an upper photoresist film. Good lithographic etching characteristics are obtained at the time of the photoresist composition. Further, the (B 1 ) component can be added in a large amount to the photoresist composition used in the formation method of the resist pattern which comprises the step of the immersion exposure or the step of forming the three-layer photoresist. It is presumed that it is a cause of high transparency (inhibition of absorption of light) in the exposure wavelength region (particularly, the wavelength region of the ArF excimer laser). (B) The components may be used alone or in combination of two or more. In the photoresist composition of the present invention, the content of the (B 1 ) component in the entire component (B) is preferably 40% by mass or more, more preferably 70% by mass or more, and particularly preferably 100% by mass. When the lower limit of the range is above ,, a good photoresist pattern shape can be obtained. In particular, when the photoresist composition for immersion exposure or the photoresist composition for forming an upper photoresist film is used to form a photoresist pattern, the lithography characteristics can be improved. When a three-layer photoresist layer is formed, -55-200821292 is preferable because it has good adhesion to a film under the photoresist, and it is possible to suppress edge curling of the photoresist pattern. Further, in the resist composition of the present invention, the content of the component (B 1 ) is preferably from 1 to 30 parts by mass, and from 5 to 20 parts by mass, based on 100 parts by mass of the component (A). More preferably, it is particularly good in 7 to 18 parts by mass. When the lower limit of the range is 値 or more, in particular, when the photoresist composition for immersion exposure or the photoresist composition for forming an upper photoresist film is used to form the photoresist pattern φ, the lithography characteristics can be improved. Also, when the upper limit is less than 値, good preservation stability can be obtained. In the component (B), the acid generator (B2) other than the above (B1) component (hereinafter also referred to as (B2) component) may be the same as the component (B2) of the above (B1) component as long as the above (B1) The component other than the component is not particularly limited, and the component which has been proposed so far as an acid generator for enhancing chemical resist can be used. ® The above-mentioned acid generator, such as a key salt acid generator such as an iron iodide salt or a phosphonium salt, an 'oxime sulfonate acid generator, a dialkyl or a bisarylsulfonyl diazo compound, a poly( Disulfonyl) diazomethane acid generator such as diazomethane, nitrobenzyl sulfonate acid generator, iminosulfonate acid generator, diphosgene acid generator, etc. Compounds are known. The iron salt-based acid generator is, for example, an acid generator represented by the following formula (). -56- 200821292 [化37]

[wherein, R51 is a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated group; R52 is a hydrogen atom, a transatom, a halogen atom, or a straight a chain or branched chain alkyl group, a linear or branched chain halogenated alkyl group, or a linear or branched alkoxy group; R53 is an aryl group which may have a substituent; U" is 1 to In the formula (bo), R51 is a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group. The branched chain alkyl group is preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 8, and most preferably a carbon number of 1 to 4. The above cyclic alkyl group has a carbon number of 4 It is preferably as high as 12, preferably from 5 to 10 carbon atoms, and particularly preferably from 6 to 10 carbon atoms. The above linear or branched fluorinated alkyl group has a carbon number of 1 to 1 〇 Preferably, those having a carbon number of 1 to 8 are more preferred, and those having a carbon number of 1 to 4 are most preferred. The cyclic fluorinated alkyl group is preferably a carbon number of 4 to 12 and a carbon number of 5 It is optimal to 10, and it is particularly preferable to have a carbon number of 6 to 10. Further, the aforementioned fluorinated alkyl group The ratio (the ratio of the number of substituted fluorine atoms to the number of all hydrogen atoms in the alkyl group) is preferably from 1 to 100%, more preferably from 50 to 100%, particularly all of the hydrogen atoms are The fluorine atom is substituted for the obtained one, and it is more preferable to increase the strength of the acid. -57- 200821292 R51 is preferably a linear hospital base or a fluoride base. &lt; R52 is a hydrogen atom, a hydroxyl group, a halogen atom, a linear alkyl group, a linear or branched chain halogenated alkyl group, or a chain alkoxy group. In R52, a halogen atom such as a fluorine atom or a brominated iodide atom is preferably a fluorine atom. Wherein the alkyl group is linear or branched, and it is from _ to 5, more preferably from 1 to 4, most preferably from 1 to 3. In R52, the alkyl group is halogenated, and at least one of the alkyl groups is substituted by a halogen atom. The alkyl group, for example, is the same as the "hospital base". The contents of the halogen atom substituted, the halogen atom are the same. It is more preferred that all of the halogenated alkyl groups are substituted by a halogen atom in an amount of 50 to 100%. In R52, the alkoxy group is linear or branched, _1 to 5, particularly 1 to 4, most preferably 1 to 3. R52, wherein a hydrogen atom is preferred. R53 is an aryl group which may have a substituent, and the structure of the removal (parent ring) may be removed, for example, a naphthyl group, a phenyl group, an effect of the invention, or an exposure light such as an ArF excimer laser, preferably a phenyl group. . a substituent such as a transbasic group or a lower-grade dean (a linear form preferably has a carbon number of 1 or more and 5 or less, and an aryl group of methyl horse R5 3 , preferably a group having no substituent or a branched chain The linear or branched, chlorine atom, carbon number is preferably 1 hydrogen atom or all of the above R52, for example, the above-mentioned ", the hydrogen atom is preferred, and the carbon number is preferably a basic ring.蒽基等, etc., from the perspective of absorption, etc.: or branched chain, better), etc. -58- 200821292 u" is an integer from 1 to 3, and 2 or 3 is better, especially 3 is the most good. Preferred examples of the acid generator represented by the formula (b-0) are as shown below. [化38]

The acid generator represented by the formula (b-Ο) may be used singly or in combination of two or more. Further, the key salt-based acid generator other than the acid generator represented by the above formula (b-Ο) is, for example, a compound represented by the following formula (b-Ι) or (b-2). [化39]

Wherein R1" to R3", R5" and R6" are each independently an aryl group or an alkyl group; -59- 200821292 R4'' is a linear, branched or cyclic alkyl group or a fluorinated alkyl group. At least one of R1" to R3'' is an aryl group; at least one of ^" and R6" is an aryl group] wherein, in the formula (b-Ι), R1" to R3'' are each independently an aryl group or an alkane. At least one of R1'' to R3" is an aryl group. Among R1" to R3", two or more aryl groups are preferred, and those in which R1'' to R3'' are all aryl groups are preferred. The aryl group of R1" to R3" is not particularly limited, and is, for example, an aryl group having 6 to 20 carbon atoms, and at least one or all of hydrogen atoms of the aryl group may be an alkane group or an alkoxy group. The halogen atom or the like may be substituted or unsubstituted. From the viewpoint of inexpensive synthesis of the aryl group, it is preferred to use an aryl group having 6 to 10 carbon atoms, and specific examples thereof include a phenyl group and a naphthyl group. The alkyl group which may be substituted for the hydrogen atom of the above aryl group is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group. Can replace the hydrogen atom of the aforementioned aryl group The alkoxy group has a carbon number of i to 5; (: an anthraceneoxy group is preferred, and a methoxy group and an ethoxy group are preferred.) The aforementioned halogen atom which can replace the hydrogen atom of the aforementioned aryl group, The atom is preferably the alkyl group of R1 $ R3", and is not particularly limited, and may be, for example, a carbon number of 1 Μ 1 G 0; a chain, a branched chain or a cyclic alkyl group, etc. Specifically, for example, Base, ethyl, propyl, isopropyl, η-butyl, isobutyl, η-pentyl, cyclopentyl, decyl, cyclohexyl, decyl, fluorenyl, etc., have excellent analytical properties, etc. In terms of carbon number 1 to 5, it is preferable to use a methyl group from the viewpoint of excellent @ 'I stomach_valence synthesis. # Φ Χ to R3" are respectively a phenyl group or a naphthyl group. -60- 200821292 R4" is a linear, branched or cyclic alkyl ' or a fluorinated alkyl group. The linear or branched chain of the above-mentioned linear group, with a carbon number of 1 to 10. Preferably, those having a carbon number of 1 to 8 are more preferably those having a carbon number of 1 to 4. The above cyclic alkyl group is a cyclic group represented by the above R1 '', which has a carbon number of 4 It is better to 1 to 5, with a carbon number of 4 to 1 0 More preferably, the carbon number is 6 to 1 Torr. 0 The linear or branched fluorinated alkyl group is preferably a carbon number of 1 to 10, and a carbon number of 1 to 8. Preferably, the carbon number is from 1 to 4, preferably the above-mentioned cyclic fluorinated alkyl group, preferably having a carbon number of 4 to 15 and more preferably having a carbon number of 4 to 10, and having a carbon number of 6 to 10. Further, the fluorination ratio of the fluorinated alkyl group (the ratio of the fluorine atom in the alkyl group) is preferably from 10 to 1% by weight, more preferably from 50 to 100%, particularly in the case where the hydrogen atom is entirely fluorine. The substitution of the atom is preferred because the acid strength is stronger. • R4'' is preferably a linear or cyclic alkyl group or a linear or cyclic fluorinated alkyl group. In the formula (b-2), R5" to R6" are each independently an aryl group or an alkyl group; at least one of R5" to R6'' is an aryl group, and all of R5'' to R6'' are aryl groups. The aryl group of R5'' and R6" is, for example, the same group as the aryl group of R1'' to R3". The alkyl group of R5'' and R6", for example, the alkyl group of R1" to R3" For the same base. -61 - 200821292 Among them, it is preferable that all of R5'' and R6'' are phenyl groups. R4" in the above formula (b_2) is the same as R4" in (b-Ι). Specific examples of the key salt acid generators represented by the formulae (b-1) and (b-2), for example, diphenyliodide trifluoromethanesulfonate or nonafluorobutanesulfonate, bis(4-tert) - butylphenyl) iodine trifluoromethanesulfonate or nonafluorobutane sulfonate, triphenylsulfonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or φ its nonafluorobutane sulfonic acid Ethyl ester, tris(4-methylphenyl)phosphonium trifluoromethanesulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, dimethyl(4-hydroxynaphthyl)phosphonium trifluoromethane a sulfonate, a heptafluoropropane sulfonate or a nonafluorobutane sulfonate thereof, a triphenylmethanesulfonate of monophenyldimethylhydrazine, a heptafluoropropane sulfonate or a nonafluorobutane sulfonate thereof, a trifluoromethanesulfonate of phenylmonomethylhydrazine, a heptafluoropropanesulfonate or a nonafluorobutanesulfonate thereof, a trifluoromethanesulfonate of (4-methylphenyl)diphenylphosphonium, Heptafluoropropane sulfonate or its nonafluorobutane sulfonate, (4-methoxyphenyl•)diphenylphosphonium trifluoromethanesulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate ,three (4-tert-butyl)phenyl hydrazine trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, diphenyl (1 -(4-methoxy)naphthyl) a trifluoromethanesulfonate, a heptafluoropropanesulfonate or a nonafluorobutanesulfonate thereof, a tris(1-naphthyl)phenylphosphonium trifluoromethanesulfonate, or a heptafluoropropanesulfonate thereof Nonafluorobutane sulfonate and the like. Further, as the anion portion of the above-mentioned key salt, a key salt substituted with a methanesulfonate, η-propanesulfonate, η-butanesulfonate or η-octanesulfonate can be used. Further, it is also possible to use a key obtained by substituting an anion moiety represented by the following general formula (b-3) or (b-4) in the above formula (bl) or (b-2); The salt acid generator may be the same (the cationic moiety is the same as the above formula (b-1丨^^b-2)). In the present specification, the oxime sulfonate-based acid generator has, for example, a compound having at least a group of 丨_formula (B·1), which has a property of generating an acid by irradiation of the radiant spring. The above-mentioned oxime sulfonate-based acid generator is often used in a ^ # enhanced chemical type positive resist composition, and the present invention can be optionally used. -C==:N—Ο—S〇2 R31 R32 (B-1) [In the formula (Bl), R31 and R32 are each independently an organic group] The organic groups of R31 and R32 are carbon atoms. Further, it may contain an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (a fluorine atom, a chlorine atom, etc.)). The organic group of R31 is preferably a linear, branched or cyclic alkyl or aryl group. The aforementioned alkyl group or aryl group may have a substituent. The substituent is not particularly limited and may, for example, be a fluorine atom, a linear one having a carbon number of 1 to 6, a branched or a cyclic alkyl group or the like. Here, the "having a substituent" means that at least one of the hydrogen atoms of the alkyl group or the aryl group which is an organic group of R31 is substituted with a substituent. The alkyl group of R31 is preferably a carbon number of 1 to 20, preferably a carbon number of 1 to -63 to 200821292 1 ,, more preferably a carbon number of 1 to 8, and a carbon number of 1 to 6. It is particularly good at carbon numbers 1 to 4. Among them, the alkyl group of R31 is particularly preferably an alkyl group obtained by partial or complete halogenation. Further, a partially halogenated alkyl group means an alkyl group in which at least one hydrogen atom is substituted by a halogen atom, and a completely halogenated alkyl group means a group in which all hydrogen atoms are replaced by a halogen atom. The halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, is preferably a fluorine atom. That is, the halogenated alkyl group is preferably a fluorinated Φ alkyl group. The aryl group of the organic group of R31 is preferably a carbon number of 4 to 20, preferably a carbon number of 4 to 10, and more preferably a carbon number of 6 to 10. The aryl group of the organic group of R31 is particularly preferably an aryl group obtained by partially or completely halogenating. Further, a partially halogenated aryl group means an aryl group in which at least one hydrogen atom is replaced by a halogen atom, and a completely halogenated aryl group means an aryl group in which all hydrogen atoms are replaced by a halogen atom. A halogen atom, for example, a fluorine atom, a chlorine atom, a desert atom, an atom, or the like, is preferably a fluorine atom. • R31 is particularly preferably an alkyl group having 1 to 4 carbon atoms which has no substituent, or a fluorinated alkyl group having 1 to 4 carbon atoms. The organic group of R32 is preferably a linear, branched or cyclic alkyl group, an aryl group or a cyano group. The alkyl group and the aryl group of R32 are, for example, the same as those of the alkyl group and the aryl group listed in the above R31. R32 is particularly preferably a cyano group, an alkyl group having 1 to 8 carbon atoms which has no substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms. The oxime sulfonate-based acid generator is more preferably a compound represented by the following formula (Β-2) or (Β-3). -64- 200821292 R34-C=N-Ο-S〇2—R35 R33 _·_(Β—2) [In the formula (B-2), R33 is a cyano group and has no substituent. Or a halogenated alkyl group; R34 is an aryl group; R35 is an alkyl group having no substituent or a halogenated alkyl group] R37-C=N-Ο一S02-R38 d36 • ”p&quot;...(曰一3 [In the formula (B-3), R36 is a cyano group, an alkyl group having no substituent or a halogenated alkyl group; R37 is a 2 or 3 valent aromatic hydrocarbon group; and R38 is an alkyl group having no substituent or an alkyl halide; The base, P" is 2 or 3] In the above formula (B-2), the alkyl group or the halogenated alkyl group having no substituent of R33 is preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 8. The carbon number is preferably from 1 to 6. The halogen atom in the halogenated alkyl group, such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. R33 is preferably a halogenated alkyl group, and more preferably a fluorinated alkyl group. The fluorinated alkyl group in R33 preferably has a hydrogen atom in the alkyl group of 50% or more, more preferably 70% or more, and more preferably 90% or more of the fluorinated group. , for example, phenyl or biphenyl, fluorenyl-65-200821292 (fluorenyl), naphthalene a ring of an aromatic hydrocarbon such as an anthracyl group or an phenanthroline group, which removes one hydrogen atom, and a part of a carbon atom constituting the ring of the aforementioned group is an oxygen atom, a sulfur atom or a nitrogen atom. The heteroaryl group is substituted with the obtained heteroaryl group, etc., wherein the fluorenyl group is more preferably. The aryl group of R3 4 may have an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having a carbon number of 10 to 10, and a carbon number of 1. A substituent such as an alkoxy group of 10 may be used. A halogen atom in a halogenated alkyl group, such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., a substituent or a halogenated group in the substituent, having a carbon number of 1 Preferably, it is preferably from 8 to 4, and more preferably, the halogenated alkyl group is a fluorinated alkyl group. The alkyl group or the halogenated alkyl group having no substituent of R3 5 is a carbon number of 1 to Preferably, 10 is more preferably a carbon number of 1 to 8, and most preferably a carbon number of 1 to 6. A halogen atom in the halogenated alkyl group, such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. R35 is an alkyl halide. The base is preferably a fluorinated alkyl group. 9 A fluorinated alkyl group in R35, wherein a hydrogen atom in the alkyl group is more preferably 50% or more, more preferably 70% or more. When 90% or more is fluorinated, it is more preferable to increase the acid produced. The most preferred one is a perfluorinated alkyl group in which 100% of hydrogen atoms are replaced by fluorine. In the above formula (B-3), R36 The alkyl group or the halogenated alkyl group having no substituent is, for example, the same as the alkyl group or the halogenated alkyl group having no substituent represented by the above R33. The 2 or 3 valent aromatic hydrocarbon group of R37 is, for example, the above R34 The base or the like obtained by removing 1 or 2 hydrogen atoms from the aryl group. -66- 200821292 The alkyl group or the alkyl group having no substituent of R38, for example, the same as the alkyl group or the halogenated alkyl group having no substituent represented by the above R35. The content 〇P" is preferably 2. Specific examples of the sulfonate-based acid generator, such as α-(p-toluenesulfonyloxyimino)-cyanide, α-(p-chlorophenylsulfonyloxyimino)- Benzyl cyanide, α-(4-nitrobenzenesulfonyloxy)-mercapto amide, &lt;2 -(4-nitro-2,dimethylbenzenesulfonyloxyimino) )-Benzyl cyanide, α-(phenylsulfonyloxyimino)-tetrachloro-based cyanide, α-(benzene-fluorenyloxyimido)-2,4-in-1 base-based gas , α-(benzene ore oxyimino)- 2,6-dichloro-based cyanide, α-(phenylsulfonyloxyimino)-1,4-methoxylated cyanide, α- (2-Chlorophenylsulfonyloxyimino)-1,4-methoxylated cyanide, α-(phenylsulfonyloxyimino)-thia- 2-acetonitrile, α-(4-10 Dialkylbenzenesulfonyloxyimido)-benzyl cyanide, α- [(ρ-toluenesulfonyloxyimino)-4-ylmethoxyphenyl]acetonitrile, α-[(dodecylbenzenesulfonyloxyimino)-4-methoxyphenyl]acetonitrile, --(p-toluenesulfonyloxyimino)-tetramethylthiocyanate, α-(methylsulfonyloxyimino)-1,4-cyclopentenylacetonitrile, α-(methylsulfonate Amino)-1-cyclohexenylacetonitrile, α-(methylsulfonyloxyimino)-1-cycloheptenylacetonitrile, α-(methylsulfonyloxyimino)-1-cyclooctenyl Acetonitrile, α-(trifluoromethylsulfonyloxyimido)-1-cyclopentenylacetonitrile, α-(trifluoromethylsulfonyloxyimido)-cyclohexylacetonitrile, α-(ethylsulfonyloxy) Imino)-ethyl-67- 200821292 acetonitrile, α-(propylsulfonyloxyimino)-propylacetonitrile, α-(cyclohexylsulfonyloxyimido)-cyclopentylacetonitrile, α—( Cyclohexylsulfonyloxyl)-cyclohexylacetonitrile, 1-(cyclohexylsulfonyloxyimino)-1,4-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentene Acetonitrile, α-(isopropylsulfonate Amino)-cyclopentenylacetonitrile, α-(η-butylsulfonyloxyimido)-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclohexene Acetonitrile, a-•(isopropylsulfonyloxyimido)-1-cyclohexenylacetonitrile, α-(η-butylsulfonyloxyimino)-1 monocyclohexenylacetonitrile, α — (Methylsulfonyloxyimido)-phenylacetonitrile, α-(methylsulfonyloxyimido)-fluorenyl-methoxyphenylacetonitrile, α-(trifluoromethylsulfonyloxyimido) ) phenylacetonitrile, α-(trifluoromethylsulfonyloxyimido)-ρ-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-ρ-methoxyphenyl Acetonitrile, α-(propylsulfonyloxyimido)-ρ-methylphenylacetonitrile, ^-(methylsulfonyloxyimido)-indenyl-bromophenylacetonitrile, and the like. Φ Further, the oxime sulfonate-based acid generator disclosed in Japanese Laid-Open Patent Publication No. Hei 9 〇 〇 8554 (paragraphs [0 012] to [0014] [Chem. 18] to [Chem. 19]), WO 2004/074242Α2 ( 65 The sulfonate-based acid generator disclosed in Examples 1 to 40) on page 85 may also be used as needed. Further, for example, a compound shown below or the like is suitable. -68- 200821292 [Chem. 43]

-69-200821292 More preferably, the sulfonate-based acid generator is exemplified by, for example, the following four compounds. [化44]

Specific examples of 'dual-homogeneous or bisarylsulfonyl-diazomethanes in diazobenzene acid generators, such as bis(isopropylsulfonyl)diazomethane, bis(p-toluenesulfonyl) ) Diazoxamine, bis(ι,ι-monomethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonate) Base) diazomethane and the like. In addition, it is also suitable to use the diazomethane-based acid generator disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. . Further, a poly(disulfonyl)diazomethane, for example, a 1,3-bis(phenyl mineral acid-diazomethylsulfonyl)propane, 1 of pp pp: 11-322707 , 4-bis(phenylsulfonyldiazomethylsulfonyl)butane, 1,6-bis(phenylsulfonyldiazomethylsulfonyl)hexane, 1,10-bis(benzene Alkylsulfonyldiazomethylsulfonyl)decane, 1,2-bis(cyclohexylsulfonyldiazomethylsulfonyl)ethane, 1,3-bis(cyclohexyl-70-200821292 Sulfonyldiazomethylsulfonyl)propane, 1,6-bis(cyclohexylsulfonyldiazomethylsulfonyl)hexane, I10-bis(cyclohexylsulfonyldiazomethylsulfonate) Base) decane, etc. (B2) The above-mentioned acid generator may be used alone or in combination of two or more. The content of the component (B) in the photoresist composition of the present invention is 0.5 to 30 parts by mass, preferably 1 to 20 parts by mass, per 100 parts by mass of the component (A). In the above range, the pattern can be sufficiently formed. A uniform solution is obtained with good preservation stability. &lt; (D) Component&gt; In the photoresist composition of the present invention, the post exposure stability of the latent image formed by the pattern- wise exposure of the resist When layer is added, a nitrogen-containing organic compound (D) of any composition (hereinafter also referred to as (D) component) may be further added. As the component (D), there have been proposals for various compounds, and it is also possible to use any of the known components, and among them, an aliphatic amine, particularly a secondary aliphatic amine or a tertiary aliphatic amine is preferred. In the specification and the scope of the patent application, the "aliphatic" is a concept related to aromaticity, that is, it is defined as a group or a compound having no aromaticity. The "aliphatic cyclic group" is defined as a monocyclic group or a polycyclic group having no aromaticity. An amine (alkylamine or alkanolamine) or a cyclic amine obtained by substituting an aliphatic amine such as at least one hydrogen atom of ammonia nh3 with an alkyl group or a hydroxyalkyl group having a carbon number of from 1 to 71 to 200821292 and less than 12 or less Wait. Specific alkylamines and alkanolamines such as n-hexylamine, n-heptylamine, η-octylamine, η-decylamine, n-decylamine, etc. monoethylamine; monoethylamine, a dialkylamine such as η-propylamine, di-n-heptylamine, -^-n-羊基月女, dicyclohexylamine; trimethylamine, triethylamine, trinium n-propyl Base amine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine, tri-n-heptylamine, tris-n-octylamine, tris-n-decyl Amine, tris-n-decylamine, triamp η - 12-yard amines, di-thylamine, monoethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octylamine An alkanolamine such as tris-octanolamine. Among them, a dimercaptoamine having a carbon number of 5 to 1 为 is preferred. The bis-η-pentylamine and the bis- y-leg base are more preferred, and the tri-n-pentylamine is most preferred. The cyclic amine is, for example, a heterocyclic compound containing a nitrogen atom as a hetero atom. The heterocyclic compound may be a monocyclic compound (aliphatic monocyclic amine) or a polycyclic compound (aliphatic polycyclic amine). An aliphatic monocyclic amine, specifically, for example, piperidine, piperazine, or the like. An aliphatic polycyclic amine, preferably having a carbon number of 6 to 10', specifically, for example, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diaza Bicyclo [5.4.0] — 7 — undecene, hexamethylenetetrazole, 1,4-diazabicyclo[2·2·2]octane, and the like. They may be used alone or in combination of two or more. (D) The component (A) component is 100 parts by mass, and is generally in the range of -72 to 200821292 0.01 to 5.0 parts by mass. &lt;Optional Component&gt; Further, the photoresist composition of the present invention is used to prevent deterioration of sensitivity, or to improve the shape of the photoresist pattern and post exposure stability of the latent image formed by the Pattern-wise exposure of the resist φ layer), etc., may further add at least one compound (E) selected from the group consisting of an organic carboxylic acid or a phosphorus oxyacid or a derivative thereof (hereinafter also Called the (E) component). An organic carboxylic acid such as acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid or the like is preferred. Phosphorus oxyacids such as phosphoric acid, phosphonic acid (P h 〇 s p h ο n i c a c i d ), phosphinic acid (Ph〇sphinic acid), etc., of which phosphonic acid is preferred. The oxo acid derivative of phosphoric acid, for example, an ester group obtained by substituting a hydrogen atom of the oxo acid with a hydrocarbon group, and the hydrocarbon group, for example, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 15 carbon atoms, or the like . The phosphoric acid derivative is, for example, a phosphoric acid ester such as di-n-butyl phosphate or diphenyl phosphate. 'Phosphonic acid derivatives such as dimethyl phosphonate, di-n-butyl phosphinate, phenylphosphonic acid, diphenyl phosphonate, diphenyl phosphonate and the like. Phosphinic acid derivatives such as phosphinates such as phenylphosphinic acid. -73- 200821292 (E) The components may be used singly or in combination of two or more. The component (E) is preferably an organic carboxylic acid, particularly salicylic acid. - The component (E) is usually used in an amount of from 1 to 5.0 parts by mass based on 1 part by mass of the component (A). The photoresist composition of the present invention may be further blended with an additive having a blending property, for example, an additive resin which can improve the properties of the photoresist film, a surfactant for improving coating properties, a dissolution inhibitor, a plasticizer, Stabilizers, colorants, halo inhibitors, dyes, etc. The photoresist composition of the third aspect of the present invention can be produced by dissolving a material in an organic solvent (hereinafter also referred to as (S) component). The (S) component may be used as long as it can dissolve the components to be used in a uniform manner. For example, one or two or more kinds of the above-mentioned known solvents can be used as the chemistries. For example, lactones such as r-butyrolactone, ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentanone, methyl isoamyl ketone, and 2-heptanone; Polyols such as diethylene glycol, propylene glycol, dipropylene glycol and derivatives thereof; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, etc. An ester-bonded compound; a monoalkyl ether or a monophenyl ether such as a monomethyl ether, a monoethyl ether, a monopropyl ether or a monobutyl ether of the above polyol or the ester-bonded compound; a derivative of a polyol such as an ether-bonded compound [wherein, propylene glycol monomethyl-74-200821292-ether ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) is preferred]; dioxane, etc. Cyclic ethers; or methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethoxylate Ester such as ethyl propionate; anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenyl ether, butyl phenyl ether Ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, trimethylbenzene • aromatic organic solvent and the like. These organic solvents may be used singly or in combination of two or more. Further, among them, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethyl lactate (EL), and T-butyrolactone are preferably used. Further, a mixed solvent obtained by mixing PGMEA with a polar solvent is preferred, and the addition ratio (mass ratio) may be appropriately determined depending on the phase and solubility of PGMEA and a polar solvent, and is preferably 1:9 to 9: 1, more preferably 2: 8 to 8: 2 range. More specifically, when the polar solvent is ethyl phthalate (EL), the mass of PGMEA: EL is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. The polar solvent is a mass ratio of PGMEA: PGME when PGME is used, preferably 1:9 to 9:1, more preferably 2··8 to 8·· 2, and most preferably 3:7 to 7:3. Further, as the component (S), for example, a mixed solvent obtained by using at least one selected from PGMEA and EL and r-butyrolactone is preferred. At this time -75-200821292, the mixing ratio, the mass ratio of the former to the latter, preferably 70: 30 to 95: 5 °, (S) component, to use the above mixed solvent of PGMEA and PGME, and r - The mixed solvent obtained from butyrolactone is preferred. The amount of the component (S) is not particularly limited. Generally, it can be appropriately selected in accordance with the concentration applied to the substrate, the thickness of the coating film, etc., and the solid concentration in the photoresist composition is generally 2 to 20 % by mass, used in the range of 5 to 15% by mass. The photoresist composition of the present invention is suitably used as a photoresist composition for immersion exposure even in a method for forming a photoresist pattern containing an immersion exposure process, and good lithography characteristics can be obtained. Further, in the method for forming a photoresist pattern containing a three-layer photoresist layer, the photoresist composition of the present invention is also suitably used as a positive photoresist composition for forming an upper photoresist film, and can be obtained well. The lithography etching characteristics. The foregoing reason is still unclear, but it is presumed that the acid generator (B1) formed by the above-mentioned compound represented by the formula (bl-3) used in the present invention is in the exposure wavelength band (especially the ArF excimer laser). In the wavelength region, the absorption of light can be effectively suppressed, and the organic solvent (photoresist solvent) used for dissolving various components of the photoresist has an effect of excellent solubility. Therefore, when the (B 1 ) component is added to the photoresist composition of the present invention, light absorption can be suppressed and the transparency of the photoresist composition can be improved. Further, the (B 1 ) component has a good dispersibility in the photoresist film, so that a more uniform distribution can be obtained in the photoresist film as compared with the conventional acid generator. Therefore, when an acid which causes the component (B1) to be generated by exposure is used, it is presumed that a more uniform diffusion can be obtained in the photoresist film when compared with the case of using a conventional acid generator. For the above reasons, it is known that the photoresist composition of the present invention can be suitably used as a resist composition for immersion exposure even in a method for forming a photoresist pattern containing an immersion exposure process. Photolithography etching characteristics. Further, in the method for forming a photoresist pattern containing a three-layer photoresist layer, the photoresist composition of the present invention is also suitably used as a positive photoresist composition for forming an upper photo-resist film. Good lithography characteristics. Further, the photoresist composition of the present invention can be formed, for example, to have a good line width uniformity (LWR), a photoresist pattern shape (especially a surface roughness of a photoresist pattern), and a mask error factor (MEF). ), exposure latitude (EL latitude) and other lithography characteristics of the photoresist pattern, MEF is, under the same exposure, fixed pitch state, change the mask size (line width and space width) When the reticle pattern of different sizes can faithfully reproduce the parameters, the closer the MEF is to the light, the higher the reproducibility of the hood. The EL latitude is a parameter of the amount of change in the size of the pattern displayed by the change in the amount of exposure, and the larger the number, the smaller the amount of change. <<Method of Forming Photoresist Pattern>> Next, a description will be given of a method of forming a photoresist pattern of a fourth embodiment of the present invention. -77-200821292 The method for forming a photoresist pattern of the present invention is a step of forming a photoresist film on a substrate by using the photoresist composition of the third embodiment of the present invention, and the photoresist film is formed. The step of exposing, the step of developing the photoresist film to form a photoresist pattern. An example of a method for forming a photoresist pattern of the present invention, for example, a method for forming a photoresist pattern containing an immersion exposure (immersion lithography) process, and a process for forming a photoresist layer having a three-layer photoresist layer The formation method of the photoresist pattern. It will be explained in detail below. &lt;Formation method of photoresist pattern containing immersion exposure process&gt; First, a photoresist composition of a third embodiment of the present invention is formed on a substrate such as a germanium wafer (in this case, Also known as a photoresist composition for immersion exposure, after coating with a spin coater or the like, and then subjected to a post-bake (PAB) treatment, β 卩 can form a photoresist film. At this time, an organic or inorganic antireflection film may be provided between the substrate and the coating layer of the photoresist composition to form a two-layer laminate. Further, a top coat film may be provided on the photoresist film. The top coat film is not particularly limited, and it can be used as usual for immersion exposure. For example, the protective film disclosed in the specification of International Publication No. 2005/01 9937, International Publication No. 2004/074937; containing -Q-NH-S02-R5 (wherein Q is a linear or branched carbon number of 1 to 5) a resin having a chain-like alkyl group, R5 is a fluorinated alkyl group, and -C0-0-R7 (wherein R7 is a fluorinated alkyl group) is dissolved in an organic solvent-78- 200821292 A protective film formed of a composition obtained by an agent (an alcohol solvent such as isobutanol), etc., wherein the "main chain cyclic resin" means that the structural unit constituting the resin is a single ring or a polycyclic ring. In the ring structure, at least one, preferably two or more carbon atoms on the ring of the ring structure are structural units constituting the main chain (hereinafter referred to as "main chain ring type structural unit"). a chain-shaped structural unit such as a polycyclic olefin (polycyclic olefin) • a structural unit derived, a structural unit containing a dicarboxylic anhydride, etc., wherein the main chain has a polycyclic olefin (polycyclic olefin, Preferably, it is preferably a structural unit derived from raw spinel or the like. The top layer coated on the photoresist film The film is preferably one which is soluble in an alkali developing solution. The steps up to now can be carried out by a known method, and the operating conditions and the like are used in accordance with the composition or characteristics of the resist composition for immersion exposure to be used. Appropriate setting is preferred. • In the formation method of the photoresist pattern containing the immersion exposure process, secondly, the photoresist film obtained by the above method is subjected to selective immersion exposure through the desired reticle pattern ( Liquid Immersion Lithography) In this case, a solvent (infiltration medium) having a refractive index higher than that of air can be filled between the photoresist film (or the top coating film) and the lens at the lowest position of the exposure device. The exposure is performed in this state (immersion exposure). The wavelength used for the exposure is not particularly limited, and it can be performed using radiation such as an ArF excimer laser, a KrF excimer laser, or an F2 laser. 79-200821292 The positive-type photoresist composition of the present invention is effective for KrF or ArF excimer lasers, particularly ArF excimer lasers. As described above, in the formation method of the present invention, exposure The immersion medium is filled between the photoresist film (or the top coating film) and the lowermost position of the exposure device and the lens, and exposure (immersion exposure) is performed in this state. At this time, the immersion medium uses refraction. The solvent having a refractive index larger than that of air and smaller than the refractive index of the photoresist film formed by using the positive-type resist composition for immersion exposure is preferable. The refractive index of the solvent is as long as the above range The solvent having a refractive index greater than that of air and smaller than the refractive index of the photoresist film, for example, water, a fluorine-based inert liquid, an anthraquinone solvent, etc. Specific examples of the fluorine-based inert liquid such as C3HC12F5 A liquid such as a fluorine-based compound such as C4F9〇CH3, C4F9OC2H5 or C5H3F7 is preferably a liquid having a boiling point of from 7 1 to 180 ° C, and more preferably from 80 to 160 ° C. In the fluorine-based inert liquid, when the boiling point is in the above range, the medium used for the wetting type can be removed by a simple method after the end of the exposure, and is preferably a fluorene-fluorine-based inert liquid, particularly in an alkyl group. A perfluoroalkyl compound obtained by substituting all hydrogen atoms with a fluorine atom is preferred. A perfluoroalkyl compound, specifically, for example, a perfluoroalkyl ether compound or a perfluoroalkylamine compound. Further, specifically, the perfluoroalkyl ether compound is, for example, perfluoro(2-butyl-tetrahydrofuran) (boiling point: 1 〇 2 (:), the above perfluoroalkylamine compound, for example, perfluorotributylamine (boiling point: 174 ΐ:), etc. The photoresist composition of the present invention, in particular, is not susceptible to the adverse effects of water-80-200821292, and can obtain excellent sensitivity and shape of the resist pattern. In other words, a solvent having a refractive index greater than that of air has a refractive index which is optimal for water. Further, water is also preferable in terms of cost, safety, environmental and extensive use. After the completion of the immersion exposure step, post exposure bake (PEB) is carried out, followed by development treatment using an alkali developer formed of an alkaline aqueous solution. Subsequently, it is preferably washed with pure water. For washing, for example, water droplets may be sprayed or sprayed onto the surface of the substrate during rotation, and the developer on the substrate and the positive photoresist composition for immersion exposure dissolved in the developer may be washed away, followed by drying, and then the photoresist. membrane( The coating film of the photoresist composition for the lubricated exposure forms a pattern with the shape of the mask pattern to form a photoresist pattern. &lt;Formation of a photoresist pattern containing a process for forming a three-layer photoresist layer Method&gt; A method for forming a photoresist pattern containing a process for forming a three-layer photoresist layer, comprising forming an organic film which can be dry-etched under a substrate, and coating and heating the underlying organic film An intermediate layer is formed by using a material of a Si atom, and an upper layer photoresist film is formed on the intermediate layer by using the photoresist composition of the third embodiment of the present invention to form a three-layer photoresist layer, and The above-mentioned upper photoresist film is exposed to 'develop the upper photoresist film to form a photoresist pattern'. [Embodiment] -81 - 200821292 Hereinafter, the present invention will be more specifically described by way of examples, but The invention is not limited by the following examples. (Example 1) (Synthesis of Compound (bl-31)) [Chem. 45]

15.00 g of __^-t-butylphenyl sulphate: Di-t-Butylphenyliodonium Perfluorobutanesulfonate, 3.20 g of benzothiophene, 〇.17 g of copper (II) benzoate dissolved The reaction was carried out in 22.5 g of chlorobenzene at 1 1 ° C for 2 hours. After completion of the reaction, it was concentrated to dryness and dissolved in 30 g of dichloromethane. After the methylene chloride solution was washed with water, 130 g of hexane was further added as a poor solvent to the solution to obtain crystals. The crystals were dried under reduced pressure at room temperature to give 6.5 g of Compound. The compound was analyzed by 1H-NMR and 19F-NMR. 1H-NMR (CDC13, 60 0MHz, internal standard: tetramethyl decane -82·

200821292 δ (ppm ) =8.06 ( dd,1H,Hi) ,8 ),8.01(d,lH,Hg) ,7.79(t,lH,

,1H,Hh) ,7·63 ( t,1H,He) , 7.62 ,7.53 ( dd,2H,Hb ) , 1.27 ( s- 9H, I 19F-NMR ( CDC13,3 76MHz ) : 5 1 1 4 · 5, 1 2 1 · 4, 1 2 5.8. From the above results, it was confirmed that the compound had the lower [46] .04 (d, 1H, Hd Hf), 7.69 ( dd (dd, 2H, He ) la ) ° (ppm) = 80.9, the configuration shown.

Ha

Hg C4F9SO3 (Example 2) (Synthesis of Compound (bl-34)) -83- 200821292 [Chem. 47]

o=c C4F9SO3 -Cb1 — 34) 6.92g of di-t-Butylphenyliodonium Perfluorobutanesulfonate, 1.94g of 2-ethylmercaptophenylthiophene, 0.08 g of copper (II) benzoate was dissolved in 1 〇. 3 8 g of chlorobenzene, and it was reacted for 1 hour under 1 1 Torr. After the reaction was completed, 51.90 g of dibutyl ether was added to take out the crude crystals. This was dissolved in 13 g of dichloromethane, and the dichloromethane solution was washed with water, and then 90 g of dibutyl ether was added as a poor solvent to obtain a crystal. The crystals were dried under reduced pressure at room temperature to give the title compound (yield: 9 g). The compound was analyzed by 1H-NMR and 19F-NMR. h-NMR (CDC13, 600MHz, internal standard: tetramethyl decane): δ (ppm) =9·13 ( s,1H,Hh ) , 8.37 ( d,1H,Hd ),8.0 9 ( d,1 Η, H g ) , 7.8 6 ( t,1 Η,H f ) , 7.7 8 ( t ,1H,He) , 7.56 ( d,2H,He ) , 7 · 5 2 ( d,2 H,Hb ) , 2.69 ( s, 3H, Hi), 1.29 (s, 9H, Ha). 19F-NMR (CDC13, 3 76MHz): (5 (ppm) = 80.9 ^ -84- 200821292 1 14.5, 121 · 5, 125.9.

From the above results, it was confirmed that the compound had the structure shown below. (Example 3) (Synthesis of Compound (b 1 - 40 )) -85- 200821292 [Chem. 49]

F^N C4F9SO3

(b1 - 40) 4.1 g of di-t-Butylphenyliodonium Perfluorobutanesulfonate, 89.89 g of 2-methylbenzolthiophene, 0.05 g Copper (II) benzoate was dissolved in 6.5 g of chlorobenzene and reacted at 100 ° C for 1 hour and 30 minutes. After the end of the reaction, dibutyl ether (45.5 g) was added to remove the crude crystals. Dissolving it in 11 g of dichloromethane, washing the dichloromethane solution with water, adding 3 5 g of dibutyl ether and 1 5 · 0 g of hexane as a poor solvent to obtain crystals. . The crystals were dried under reduced pressure at room temperature to give the title compound. 2.20 g of the compound. The compound was analyzed by 1?-nmr and 19F-NMR. iH-NMR (CDC13, 40 0MHz, internal standard: tetramethyl decane): (5 (ppm) = 8.05 (d, 1H, Hf), 7 · 8 7 (d, 1 Η, Hi), 7·74 (t , 1H, Hh ) , 7.65 ( s, 1H, He ) , 7.60 ( m , 4H, Hd + He) , 7.54 ( t, 1H, Hg) , 2.41 ( s, 1H, Hb -86 - 200821292 ), 1 . 3 1 ( s, 9H, Ha ) 19F-NMR ( CDC13, 3 76 MHz ) : 5 (ppm) = 80·9, 114·5 , 121.5 , 125.9. From the above results, it was confirmed that the compound has the following Structure [化50]

Ha

C4F9S03&quot;&lt;SolubilityEvaluation&gt; For the above compounds (bl-31), (bl-34), (bl-40) and (1-naphthyl)phenyl mirror nonafluorobutane sulfonate ((B) -2), its solubility was evaluated in the following manner. A propylene glycol monomethyl ether acetate (PGMEA) solution, a propylene glycol monomethyl ether (PGME) solution, and a lactic acid &amp; ester (EL) solution of each compound of varying concentrations were prepared. After the adjustment, each solution was stirred to determine the concentration of each acid to give complete dissolution of the -87-200821292 agent. The results are shown in Table 1. The solubility of the above-mentioned compounds (b 1 - 3 4 ) and (b 1 - 4 0 ) in the first embodiment of the present invention for PGMEA, PGME, and EL of a general photoresist solvent was confirmed. It is superior to bis(1-naphthyl)phenylphosphonium hexafluorobutane sulfonate ((8)_2). [Table 1] Example 1 (bl -3 1) Example 2 (bl-34) Example 3 (bl-40) (B)-2 Solubility to PGMEA (% by mass) 4 5 &gt; 20 2 Pairs Solubility of PGME (% by mass) &gt;10 20 &gt; 2 0 5 Solubility to EL (% by mass) &gt;20 5 &gt; 20 5

(Example 4) (Synthesis of Compound (b 1 - 3 7 )) [Chem. 51]

C4F9SO3&quot;&quot;•(b1—37) -88- 200821292 2.85g of Di_Phenyl iodonium Perfluorobutanesulfonate and 0.80 g of 2-methylphenylhydrazine [b]thiophene 0.04 g of copper (II) benzoate was dissolved in 43 g of chlorobenzene and reacted at 110 ° C for 1 hour. After the completion of the reaction, a house was added as a poor solvent to obtain crystals. The crystals were dried under reduced pressure at room temperature to give the title compound (5 g). The compound was analyzed by 1H_NMR and 19F_NMR. Xin iH-NMRCCDClg, 400MHz, internal standard: tetramethyl sand court) · δ (ppm) =8.2 5 ( d ? Hd) , 7.96 (d, Hg), 7.87~ 7.75 (m, He, Hf'Hh), 7.69 ~ 7.63 (m, Ha, Hb, He ), 2.40 ( s, Hi ). 19F-NMR (CDC13, 376 MHz): δ (ppm) = 75 9, 110.1, 116.8, 121.1. From the above results, it was confirmed that the compound had the structure shown below.

-89- 200821292 [化52]

Ha

Hg C4F9SO3 (Examples 5 to 7 and Comparative Example 1) &lt;Resin component (A) &gt; The components (A)-1 used in Examples 5 to 7 and Comparative Example 1 are as follows. The polymer (A)-1 was synthesized. Specifically, in a flask equipped with a nitrogen gas introduction port, a stirrer, and a reactor, PGMEA was added under a nitrogen atmosphere, and the temperature in the stirring bath was raised to 80 °C. Next, 2,2'-azobisisobutyronitrile of the polymerization initiator, and PGMEA, and the monomer of each structural unit of the polymer (A)-1 (2-methyl-2-anomantyl) a monomer solution obtained by mixing methacrylate / α propylene methoxy r - butyrolactone / 3 - hydroxy - 1 - adamantyl hydrazine 2 / 5 / 2 (mole ratio), used at a certain speed The flask was slid into the flask over a period of 6 hours and then held at ° C for 1 hour. Thereafter, the reaction solution was returned to room temperature. The polymerization is carried out in the order of temperature and temperature. (AMBN-derived monomethacrylate is added dropwise, at 80-90 - 200821292. Next, the obtained reaction solution is dropped into about methanol in a stirred state to obtain a colorless precipitate precipitate. The obtained precipitate ί was precipitated and washed with about 30 times j relative to the monomer used for the polymerization. Thereafter, the precipitate was filtered off, and dried under reduced pressure at 50 ° C to obtain a polymer ( A) - 1. Further, the mass average molecular weight and the degree of dispersion (Mw/Mn) of the following polymer (A)-1 are recited therein. The mass average fraction) and the degree of dispersion (Mw/Mn) are gel permeation. The color layer is obtained based on the polystyrene conversion standard. Further, the composition ratio was calculated by carbon NMR. The figure attached to the lower right of the chemical formula is the unit of each structural unit in the polymer. Considering the amount of 30 times, about 40 • quantity (Mw) of the amount of methanol in the mash (Mw analysis method (GPC, the ratio of the structure sheet (Mo

• · · (A) — 1 (Mw : 1 0000, Mw/Mn : 2.0) &lt;Preparation of positive-type photoresist composition solution&gt; Photoresist composition The components shown in Table 2 were mixed and dissolved to make positive Type solution. -91 - 200821292 [Table 2] (A) Ingredient 151^1 Minute (D) Ingredient (E) Ingredient (s) Ingredient Example 5 (A)-l "1001 (B)-l [11.0] (D)- l [0.54] (Ε)·1 Γ1.321 (S)-l [10.0] (S)_2 [2000] Example 6 (A)-l Π〇〇1 (B)-3 [12.01 (D)- l ro.54] (E)-l ri.32] (S)-l [10.0] (S)-2 [2000] Example 7 (A)-1 『1〇〇1 (B)-4 [12.61 _t------ (D)-l Γ0.54] _ (E)-l Π.32] (S)-l rio.oi (S)-2 [20001 Comparative Example 1 (A)-l [ 1001 (B)-2 [13.01 (D)-l ro.54] _ (E)-l Π·32] (S)-l [10.0] (S)-2 [2000] The short names in Table 2 have The following meanings. Further, the number in [] is the amount of addition (parts by mass). (B) -1 : an acid generator (compound of Example 1) represented by the following chemical formula (b). (B) -3: an acid generator (compound of Example 3) represented by the following chemical formula (bl-40). (B) -4 : an acid generator represented by the following chemical formula (bl-34)

Compound of Example 2).

-92- 200821292 (B) -2 : Di(naphthyl)phenylphosphonium nonafluorobutane sulfonate. (D ) -1 : Tri-n-pentylamine. (Ε ) -1 : Salicylic acid. (s ) -1 : r - butyrolactone. (S ) -2 : PGMEA/PGME = 6/4 (mass ratio) mixed solvent. _ &lt;Evaluation of lithography etching characteristics&gt; A photoresist pattern was formed using the obtained positive-type photoresist composition solution, and the following lithographic etching property evaluation was performed. [Formation of the photoresist pattern] The organic anti-reflection film composition "ARC-29A" (manufactured by Privah Technology Co., Ltd.) was applied to a wafer of 8 inches on a wafer by a spin coater. The hot plate was baked at 205 ° C for 60 seconds, and dried to form an organic anti-reflection film having a film thickness of 77 nm. Subsequently, the positive-type photoresist composition solution obtained above is applied to the anti-reflection film by using a spin coater, and pre-fired on a hot platen at 110 ° C for 60 seconds. After baking (PAB) treatment, after drying, a photoresist film having a film thickness of 150 nm was formed. Secondly, the ArF excimer laser (1 93 nm) was selectively selected by the reticle pattern using the ArF exposure device NSR-S302 (manufactured by Ricoh Co., Ltd.; NA (number of openings) = 0.60, 2/3 wheel illumination). Irradiation. Subsequently, post-exposure heating (PEB) treatment was carried out under conditions of 1 l〇 ° C for 60 seconds, and -23 - 200821292 was further used at 23 ° C, using a 2.38 mass % aqueous solution of tetramethylammonium hydroxide (TM AH ). The development was carried out under conditions of 30 seconds, and then washed with pure water for 30 seconds, and after vibration drying, a photoresist pattern of line and space (1··1) was formed (L/S pattern). And, the most appropriate exposure amount for forming an L/S pattern having a line width of 120 nm and a pitch of 240 nm is obtained. From the above results, it was found that the photoresist compositions of Examples 5 to 7 of the present invention confirmed that a fine photoresist pattern was obtained. (Evaluation on Hard Mask) The photoresist compositions of Examples 5 to 6 and Comparative Example 1 were formed and evaluated using a photoresist pattern containing a step of forming a three-layer photoresist layer. [Formation of Photoresist Pattern] A laminate was produced in the following order, and a photoresist pattern was formed using the photoresist laminate. First, a solution of a commercially available underlying material was applied onto a 8 inch silicon wafer using a spin coater, and soft baked at 90 ° C for 90 seconds to form a film thickness of 27 Onm under the organic film. Next, a composition for forming a hard mask layer using a spin coater (phenyl sesquisulfate/hydrosesquioxane/methylsesquioxanes/methylsesquioxalate propionate copolymerization) The product obtained by dissolving in a mixed solvent of PGMEA and EL (mass ratio: 6/4) (solid content concentration: 2.5% by mass))) was applied onto the lower layer, and soft-baked at 90 ° C for 90 seconds. Subsequently, -94-200821292 was further baked at 250 ° C for 90 seconds to form a hard mask layer (intermediate layer) having a film thickness of 3 Onm. Next, for this intermediate layer, a positive photoresist composition solution of Examples 5 to 6 and Comparative Example 1 was applied thereto by using a spin coater, and then on a hot plate at a temperature of 10 ° C, Pre-baking (PAB) treatment was carried out for 60 seconds, and after drying, a positive-type photoresist layer (upper photoresist film) having a film thickness of 15 nm was formed, and a photoresist having a three-layer structure laminated on the substrate was formed. Layer φ photoresist laminate. Secondly, the ArF excimer laser (193 nm) was selectively irradiated by a reticle pattern using an ArF exposure apparatus NSR-S302 (manufactured by Ricoh Co., Ltd.; NA (number of openings) = 0.60, 2/3 wheel illumination). . Subsequently, post-exposure heating (pEB) treatment was carried out at 110 ° C for 60 seconds, and at 23 ° C, a 2.38 mass % aqueous solution of tetramethylammonium hydroxide (TMAH) was used for 30 seconds. The development was carried out, and then washed with pure water for 30 seconds, and after vibration drying, a line pattern of a line width of 1 20 nm, a pitch of 240 nm, and a space (1:1) (L/S pattern) was formed. From the above results, it is known that the photoresist compositions of Examples 5 and 6 of the present invention have a photoresist pattern obtained by a method for forming a photoresist pattern containing a process for forming a three-layer photoresist layer. The intermediate layer formed of the composition for forming a hard mask of sesquiterpene oxide has good adhesion, and it is confirmed that the edge of the photoresist pattern is suppressed. [Industrial Applicability] -95-200821292 The present invention provides a novel compound suitable as an acid generator for a photoresist composition, an acid generator formed by the compound, and a photoresist composition containing the acid generator And a method of forming a photoresist pattern using the photoresist composition. Therefore, the present invention is extremely useful in the industry.

-96-

Claims (1)

200821292 X. Applying for a patent garden [wherein R41, R42 and R43 are each independently an alkyl group, a B-group, a carboxyl group, a hydroxyl group, or a hydroxyalkyl group; an integer integer of 0 to 3' r, n3 is 0~ An integer of 2, wherein m, n2 and n3 are 〇; χ- is an anion]. 2. The compound of claim 1, wherein the compound is a halogenated alkylsulfonic acid ion. 3. An acid generator (Β1) characterized by being formed by a compound according to item 1 or 2. 4. A photoresist composition comprising a substrate component (A) which undergoes a change in acid-based solvability and a photoresist composition which produces a green component (B) via exposure, characterized in that the component (B) ) is an acid generator (B 1 ) containing a compound represented by the following formula (bl-3), 3), and the oxime 12 is 〇~3, and the above 5 Γ Acid acid production of acid to form a composition -97- 200821292 [Chemical 2] ί«41) Π1 χ — 丨43, Μ •&quot;(b1 -3) [wherein R41, R42 and r43 are each independently alkyl, ethylidene, alkane, residue, warp group Or hydroxyalkyl; ηι is an integer of 〇~3, n2 is an integer ' Π3 is an integer of 〇~2, wherein ηι, :^ and n3 are not 〇; an anion]. 5. The photoresist composition of claim 4, wherein X is a halogenated alkylsulfonate ion. 6. The photo-resist composition of claim 4, wherein the content of the acid generator (B 1 ) is in the range of 1 to 30 parts by mass relative to the substrate component (A 1 〇〇 by mass) 7. For the photoresist composition of claim 4, wherein the substrate component (A) is based on the action of an acid to increase the alkali-soluble component. 8 · The photoresist of claim 7 a composition wherein the substrate component (A) is an acid-soluble additive to increase an alkali-soluble fat component (A 1 ). 9. The photoresist composition according to claim 8 wherein the oxy group is 0 to 3 At the same time, '刖, 前前', the former base '刖之树, 刖-98 - 200821292 The resin component (A 1 ) is a structural unit (al) derived from an acrylate having an acid-dissociable dissolution inhibiting group. 10. The photoresist composition according to claim 9, wherein the resin component (A1) contains a structural unit (a2) derived from an acrylate having a cyclic group containing a lactone. 11. The photoresist composition according to claim 9, wherein the resin component (A1) 尙 contains a structural unit (a3) derived from an acrylate having a polar group-containing aliphatic hydrocarbon group. 12. The photoresist composition according to claim 10, wherein the resin component (A1) 尙 contains a structural unit (a3) derived from an acrylate having a polar group-containing aliphatic hydrocarbon group. 1 3 . The photoresist composition of claim 4, which contains the nitrogen-containing organic compound (D). A method for forming a photoresist pattern, comprising the step of forming a photoresist film on a substrate by using the photoresist composition according to any one of claims 4 to 13 and causing the photoresist The step of film exposure is followed by the step of developing the aforementioned photoresist film to form a photoresist pattern. -99 - 200821292 VII. Designated representative map: (1) The representative representative of the case is: None (2), the representative symbol of the representative figure is simple: No 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: (M-3) -4 -